Non-canonical DNA structures: i-Motifs are four-stranded DNA structures formed by the folding of cytosine-rich sequences present in telomeres and gene promoters. Compared to complementary G-quadruplexes, i-motifs are less explored. This Minireview describes significant advances in chemically regulated i-motif-based functional nanostructures and small-molecule targeting of i-motifs for therapeutics.

Cubosomes are nanoparticles with an internal periodic lipid membrane separated by two distinct water channels. The surface is stabilized by a polymer outer corona. Recent advances have enabled the rational design of cubosome systems. Key considerations are outlined for engineering cubosomes for tailor-made applications including delivery, biosensing, and medical applications.

Next-generation metallodrugs: This Review aims to critically evaluate the potential of polyoxometalates, especially organically functionalized hybrid and nanocomposite structures, as future clinically applied metallodrugs in the combat against cancer.

Testing the water: The microscopic interplay between cations, anions, and water can be understood by THz-FTIR spectroscopy. Dissection of the spectra shows that the full response of the solvating water when dissolving salts can not be explained from the individual properties (such as the ion radius, the ion–water interaction, the structural hydration shell size, etc.) alone; cooperativity effects need to be included.

Bulk up: The first catalytic asymmetric construction of 3,3′-bisindole skeletons bearing axial and central chirality has been established by organocatalytic asymmetric addition reactions of 2-substituted 3,3′-bisindoles with electrophiles. This reaction also represents the first highly enantioselective construction of axially chiral 3,3′-bisindole skeletons, and utilizes the strategy of introducing a bulky group to the ortho-position of prochiral 3,3′-bisindoles.

Growing on U: Large U^IV clusters slowly assemble in organic solution, upon controlled hydrolysis of UCl₄, from a hexanuclear {U₆} cluster. The process is time dependent and is affected by temperature and added base.

Gold complexes: Multistimuli-responsive benzo[b]phosphole alkynylgold(I) complexes have been prepared. The complexes display photochromism and mechanochromism. In addition, robust fatigue resistance and excellent thermal irreversibility of the photoresponsive gold(I) complexes have been realized.

Tetrahedrally coordinated blende CoO and octahedrally coordinated rocksalt CoO atomic layers with similar thicknesses were synthesized. The blende CoO atomic layers achieve boosted visible-light-driven H₂ and O₂ formation rates that are roughly 3.7 times higher than those of the rocksalt CoO atomic layers.

Taming oxygen for effective cleavage of the O−O bond and a further C−O bond formation has been achieved through proton transfer/electron transfer steps. A free radical mechanism accounts for the transformation of peroxide complexes into water and 2-iradaoxetane complexes (see scheme; C gray, Ir green, N blue, O red; Mepy=4-methylpyridine).

Breaking symmetry: A highly modular method to covalently transfer different DNA sequences with controllable directionality, length, and valency onto different synthetic molecules is reported. These DNA-imprinted small molecules can be elongated asymmetrically to different lengths in high yield using PCR and can be chemically replicated.

Current events: DNA-mediated long-range ET in gold-tethered DNA duplexes shows directional preference for reduction, thereby making DNA a molecular rectifier.

Cu^II–NTA spin labeling: By using Cu^II–NTA spin labeling together with DEER spectroscopy, the active state conformations of the metal regulator CueR can be captured.

Fully characterised boron complexes of porphyrazine and phthalocyanine contain FBOBF and PhBOBPh moieties in both cisoid and transoid geometries. A DFT study, extended to include the previously reported FBOBF porphyrin, corrole, and calixphyrin complexes shows that the stereochemical preferences correlate with the ease with which each macrocycle can accommodate a rectangularly distorted N₄ cavity.

A sunny outlook: A cross-linked porous conjugated polymer photosensitizer CPTF is used for sunlight-induced photooxidation. Under simulated AM 1.5G irradiation, benzaldehyde can be oxidized to benzoic acid easily on a 10 g scale in the presence of CPTF. In addition, CPTF can also be used as photocatalyst for sunlight-induced organic waste decomposition and an antibacterial agent in water.

Double trouble: Novel Y-shaped scaffolds have been synthesized, with meta-iodobenzilguanidine analogues covalently attached at each end of the Y-structure, to deliver diagnostic and therapeutic agents to neuroblastoma cells. These double-targeting agents have a strong affinity for the norepinephrine transporter, usually overexpressed on the neuroblastoma cell membrane, and accumulate in cells at a higher level than single-targeting agents.

Elementary, my dear Watson: Organellar single-molecule, high-resolution localization and counting (oSHiRLoC), a fluorescence imaging method for the quantitative mapping of the endosomal processing of cargo DNA in innate immune cells with organelle-specific resolution, is reported. By using this method, it is shown that endosomal DNA degradation occurs mainly in lysosomes and is negligible in late endosomes.

Let the sunshine in: Single-entity ordered–disordered monolayer D-HNb₃O₈ nanosheets were engineered to realize full solar spectrum (250–2500 nm) utilization. The crystalline domains absorb UV photons to generate charge carriers, while the disordered “nanoislands” capture the full spectrum for solar heating to thermally boost the reaction kinetics.

Multicolor emissive polymers: Multicolor emission was achieved in polymers that contain a switchable boron chromophore and a methacrylate backbone. The molecular weight and degree of polymerization provide the key driving force for the switching of three-coordinate boron units to four-coordinate ones in the polymer, and for the emission transition from blue to white and then red.

Now you see me: A fluorogenic probe for cell surface phosphatidylserine enables time-lapse imaging of cell death. The probe circumvents a number of drawbacks associated with commonly used annexin V cell death markers, including Ca²⁺ dependence, temperature sensitivity, and binding kinetics.

Get in touch with lithium: The generation of surface lithiophilicity on planar and 3D Cu hosts for Li metal anodes is reported. Enabled by a lattice matching of Cu(100) and Li(110), smooth deposition of Li thin films and the creation of ultra-smooth ultra-thin SEI on the Cu hosts is made possible. This allows a high utilization of not only the surface but also cavities of the Cu hosts.

Hide and seek: Markov state models are used to unveil hidden conformational states of Monoamine Oxidase from Aspergillus niger (MAO-N). These hidden conformations, not previously observed by any other technique, play a crucial role in the enzyme activity and substrate binding. This reveals how distal mutations regulate MAO-N activity by stabilizing these hidden, catalytically important conformational states.

Optimized storage: The metalation of the phenoxide–cyclohexanolate pair is a successful strategy to optimize the thermodynamic properties of this type of hydrogen storage material (see figure). In experiments the sodiated pair desorbed hydrogen at 413 K (373 K) in the solid state (aqueous solution), whereas hydrogenation could be accomplished at temperatures as low as 202 K.

Use the force: A combined rotational spectroscopic and quantum-chemical study on diphenyl ether, dibenzofuran, and fluorene determined the influence of structural flexibility and the presence of heteroatoms on aromatic dimer formation. This furthers our understanding of the first steps of molecular aggregation in aromatic systems.

Order to disorder: Ion mobility mass spectrometry is employed to measure the intrinsic dynamic properties of p27, both in isolation and within the complex with Cdk2/cyclin A, and its individual domains. The findings support the formation of a fuzzy complex in which both the N- and C-termini of p27 interact with Cdk2/cyclin A in multiple states.

Late-stage fluorination: K¹⁸F is applied in a newly developed Cu-mediated ortho-C(sp²)−H radiofluorination of aromatic carboxylic acids that are protected as 8-aminoquinoline benzamides. Fluorination of 18 examples in up to 62 % radiochemical yield and high specific activity is reported, including the automated synthesis of [¹⁸F]AC261066.

Gold nanorods, end-grafted with achiral polymer ligands, show a new mechanism of chiral surface patterning giving a helicoidal morphology. This morphology is dictated by the relationship between the polymer grafting density and the ratio of the polymer length to the nanorod radius.

Light power: CdS quantum dots/C₆₀ tubular micromotors with chemical/multi-light-controlled propulsion and “on-the-fly” chemical acceleration capabilities are described. The built-in accelerating optical system allows for the control of the velocity over the entire UV/Vis light spectrum by modulating the catalyst surface chemistry.

Long ago Zintlsized and now analyzed: ²⁹Si and ¹H NMR experiments confirm the existence of Zintl ions [μ-HSi₄]³⁻ and [Si₅]²⁻ in liquid ammonia. For [μ-HSi₄]³⁻, NMR and theoretical calculations reveal a bridging hydrogen atom forming a 3c-2e-bond. Additionally, [Si₅]²⁻, only known from solvate crystal structures so far, was characterized by ²⁹Si NMR. Here, NBO analysis indicates the formation of three localized 3c-2e-bonds.

Go direct: A hemoprotein catalyst was engineered to transform alkenes directly to amino alcohols with high enantioselectivity. Derived by directed evolution from a thermostable cytochrome c, the protein catalyst uses O-pivaloylhydroxylamine to generate a reactive iron-nitrogen species.

A chemical chameleon: γ-Azaproline was introduced as a pH-responsive and functionalizable amino acid with a conformation that can adapt to the environment. Incorporation into collagen triple helices showed its value as a tool to functionalize peptides and proteins and render them pH-responsive.

Ready to plassemble: The synthesis of TiN, ZrN, and HfN nanocrystals using solid-state metathesis is reported. The nanocrystals, which are dispersible in water, show localized surface plasmonic resonances in the near infrared (TiN) and visible region (ZrN, HfN) of light. This makes them ideal for applications like photothermal therapy or plasmon-enhanced sensing.

Enzymatic alkylation: The cylindrocyclophane biosynthetic enzyme CylK is identified as a promiscuous catalyst for Friedel–Crafts alkylation of resorcinol substrates with alkyl halide electrophiles. This transformation, which proceeds with exceptional regioselectivity and stereospecificity, highlights the promise of enzymatic catalysis for enabling mild and selective C−C bond-forming synthetic methodology.

Beam me up: A high-energy gas-cluster ion beam (GCIB) with 1 μm lateral resolution was developed. This allowed single cell and subcellular mass spectrometry imaging of diverse phospholipids, including cardiolipin (CL) and phosphatidylethanolamine (PE). Coupling this with immunohistochemistry provided assessments in specific subcellular compartments.

Carborane-based AIEgens: The reductive–oxidative aggregation-induced electrochemiluminescence (AIECL) of carboranyl carbazoles in air-saturated aqueous media was investigated. Mechanistic studies indicate that the carboranyl motif plays vital role in the high ECL intensity and stability of the aggregates.

Twice the fun: In the addition of 2,6-dimethylphenyl isocyanide or tert-butyl isocyanide to tetramesityldisilene, the initially formed product is an iminodisilirane. These iminodisilirane intermediates react with a second equivalent of the isocyanide to give a 3-silaazetidine or a bicyclic double enamine, respectively.

RAFT in water: Current limitations of polymerization-induced self-assembly (PISA) are overcome by combining reversible addition fragmentation chain transfer (RAFT) polymerization and supramolecular chemistry. The introduction of supramolecular stickers into PISA allows the robust synthesis of long nanofibres with tunable diameter.

Ring constraints: The major opportunist human pathogen Pseudomonas aeruginosa produces azetidine 2-carboxylic acid, a proline mimic, to be incorporated into a quorum-sensing controlled nonribosomal peptide synthetase assembly line, yielding constrained bicyclic alkaloids. These compounds play important functions in the physiology of P. aeruginosa.

Polymers made by an artificial brain: An autonomous continuous flow system for polymerizations is presented. Reaction parameters (i.e., residence time, monomer and control agent/initiator concentrations) are dynamically and autonomously varied with a self-optimizing algorithm to obtain predefined molecular weights. This novel platform can target molecular weights with unprecedented accuracy in a reproducible manner.

Rigid sp³ scaffolds: A catalytic and stereospecific method for the preparation of enantioenriched α-hydroxy cyclopropylboronates with control in four contiguous stereocenters is described. The reaction involves the borylation of readily available allylic epoxides using an inexpensive Cu^I salt and a commercially available phosphine ligand. High diastereocontrol is achieved and different diastereomers can be selectively prepared.

Chemo- and enantio-selective nucleophilic aryl transfer: The key reactant is a chiral tricoordinated lithium amido aryl zincate of which the chiral appendage is simply recovered and reused. The arylation leaves intact sensitive functions such as esters, nitriles, ketones or enolisable sites, while running with aldehyde groups in good yields and high ee values, this whatever the ortho, meta, or para substituent borne by the substrate if aromatic.

Under reducing conditions: A nickel-catalyzed asymmetric diarylation reaction of vinylarenes enables the preparation of chiral α,α,β-triarylated ethane scaffolds. The use of reducing conditions with aryl bromides as coupling partners obviates the need for stoichiometric organometallic reagents, and tolerates a broad range of functional groups.

Give a little bit: The ylide-functionalized phosphine ^CyY_MePCy₂, which is easy to synthesize in few steps, shows excellent performance in a series of C−N cross coupling reactions at room temperature. This efficiency can be explained by the strong electron-donating properties of the ligand and its unique architecture, which allows stabilization of the active Pd species through a weak C−H⋅⋅⋅Pd interaction.

A classic with P and N: 2H-Phospholes react in a highly chemoselective phospha-aza-Diels–Alder reaction with an activated, electron-poor imine to give a new class of compounds, namely 1-phospha-2-azanorbornenes.

Binary quantum cluster equilibrium theory was applied to predict acid strengths over the complete concentration range through mole-fraction-depended populations of molecular and ionic clusters. It is shown for formic and acetic acid dissolved in water that the acid strength increases with increasing mole fraction in a complex way, reflecting the complex interplay between the dissociated hydronium ions.

CApTive lock-key model: Oxygen heterocycles were synthesized in high enantioselectivities from pyrylium derivatives by embracing a multi-coordination approach with helical anion-binding tetrakistriazole catalysts. New insights into the hydrogen-donor ability and key binding interactions suggest the formation of a high-order host:guest complex.

A coordination compound with intact Bi₇³⁻ ligands, namely the homoleptic complex [(Bi₇)Cd(Bi₇)]⁴⁻, and the ternary cluster [(Bi₆)Zn₃(TlBi₅)]⁴⁻ were prepared through in situ degradation of the binary Zintl anion (TlBi₃)²⁻. The compounds provide a glimpse into a possible formation pathway of the polycyclic polybismuthide, the follow-up chemistry of which has been unprecedented to date. Both title compounds were further studied by means of DFT methods.