The 57th SCS Conference on Stereochemistry, better known as the Bürgenstock Conference, brought together a diverse range of chemistry expertise in Brunnen, Switzerland.

This paper highlights a smart sustainable Ni@TiO_x catalyst, Ni encapsulated in TiO_x, for propane dehydrogenation (PDH), as reported by Gong and co-workers. The catalyst demonstrates exceptional performance in PDH, achieving 94 % propylene selectivity and high stability. This design offers a cost-effective and environmentally friendly alternative to traditional noble metal-based catalysts, with potential for broader industrial applications.

This Minireview describes the most recent advances in carbonylative transformations involving heteroatom adjacent carbon radicals, specifically including the heteroatoms oxygen (O), nitrogen (N), phosphorus (P), silicon (Si), sulfur (S), boron (B), fluorine (F), and chlorine (Cl). The reaction mechanisms are also described in detail.

Sunlight has long been the primary energy source for our planet. This minireview highlights its importance and investigates the potential revolutionary impact of photocatalysis on Earth. It examines fundamental processes, including the formation of prebiotic molecules and the oxygen evolution reaction via water oxidation. Additionally, the review assesses various carbon and nitrogen-based complexes photocatalysts and their roles in driving chemical reactions. It further provides insights into possible evolutionary pathways for Earth, emphasizing the pivotal influence of carbon and nitrogen-based photocatalysts in the development of Earth.

Phototheranostics of infectious diseases by utilizing NIR-II AIEgens has been developed at a tremendous pace. This Minireview summarizes recent efforts in this area in terms of molecular design strategy and bioapplications, and discusses current challenges and promising prospects.

This review outlines the recent advances of organic cocrystals in emerging cutting-edge properties and applications during the nearest five years including PTC, RTP, TADF, CPL, OSSLs, NIR sensing, photocatalysis, batteries, and stimuli responses, along with the structure–property relationship, limitations, prospects and some inspirations for future investigations.

Enabled by excited-state intramolecular proton transfer (ESIPT) and cis-trans isomerization, visible-light-driven solid-state fluorescent photoswitch has been developed. It was obtained by incorporating a bulky naphthalimide group into a salicylaldimine. The photoswitch shows triple fluorescence switching, showing potential application in high-level information encryption.

Aza-diarylethenes with benzothiophene-S,S-dioxide as a part of the hexatriene structure undergo bidirectional thermal isomerization in addition to bidirectional photochemical isomerization due to a small energy difference between the open- and the closed-ring isomers. Kinetic analysis and theoretical calculations revealed the detailed mechanisms of the photochemical and thermal reactions. Using these unique properties, both light-writing/light-erasing and heat-writing/light-erasing systems were demonstrated.

Covalent organic frameworks (COFs) are crystalline polymeric materials featuring wide-ranging structural control and modularity. The synthesis of a series of donor-acceptor-donor Wurster building blocks enabled the formation of isostructural, photoactive COFs with distinct optical features in thin films. These COFs were further applied for photoelectrochemical water splitting.

Introducing dynamic boroxine linkers into mesoporous PCN-333 creates defects that expand pore sizes, enabling the encapsulation of enzymes larger than the inherent pore size of MOFs. This strategy allows the immobilization of glycoenzymes in MOFs for synthesizing complex oligosaccharides and polysaccharides, demonstrating high activity and enhanced enzyme stability.

Under pathophysiological hypoxic environments, the caged non-metabolizable precursor pNB-ManNAz exhibited responsiveness to cellular NTR, culminating in structural self-immolation and the resultant ManNAz could be incorporated onto the cell surface glycoproteins, thereby facilitating fluorescence labeling via bioorthogonal chemistry. This NTR-responsive metabolic reporter demonstrated broad applicability for specific hypoxia labeling in diverse cell lines, particularly in the monitoring of orthotopic tumorigenesis and targeted tumor phototherapy in zebrafish models.

A novel fullerene-based hole transport material (FHTM) has been designed and synthesized, exhibiting high hole mobility through intramolecular electron transfer. Incorporating FHTM at the NiO_x/perovskite interface optimizes the energy level alignment and improves the quality of the perovskite layer. This integration results in an inverted perovskite solar cell with a champion efficiency of 25.58 % (certified:25.04 %) and enhanced stability.

In situ time-resolved X-ray diffraction studies of electrochemical graphite oxidation in aqueous sulfuric acid reveal periodic structural changes of a graphite intercalation compound (GIC) into “pristine graphite oxide”. The potential oscillations of the graphite electrode correlate with the appearance and disappearance of a solid phase identified as stage-1 GIC. The observed phenomenon can be considered as a new type of oscillating reaction.

Iron acquisition is a crucial factor for bacterial growth, and its transport process could be a promising target for antibacterial drugs. A potent molecular inhibitor of the ferric citrate binding protein FecB has been discovered. The findings provide new insight into the modulation of ferric ion acquisition pathways and their application to pathogen growth suppression.

The commercialization of PVSCs is hindered by poor reproducibility due to the chemical instability of the solution-processed materials. We first observe that the aging phenomenon is more pronounced in the precursor solution of the two-step sequential method compared to that in the one-step method due to the difference in the used solvents. Here, an effective targeted strategy for precursor stabilization by introducing benzene-1,3-dithiol (BDT) and decamethylferrocene (FcMe₁₀) additives into the organic amine salt solution and the PbI₂ precursor solution, thus extending the shelf-life of the two-step precursor solutions.

A copper-catalyzed enantioselective dehydro-Diels–Alder reaction has been realized via vinyl cation pathway, enabling the atom-economical synthesis of axially chiral phenyl and indolyl carbazoles. This protocol continues the first example of non-noble metal-catalyzed enantioselective DDA reaction. Notably, the constructed axially chiral carbazoles are applicable to asymmetric catalysis.

The introduction of an ethylene bridge into a quaternary adamantane-type cluster core {Si(CH₂)_n(C₂H₄)_mSn₃S₃} (n/m=3/0 or 2/1) causes distinct distortions, which the molecules escape by an unprecedented dimerization of the cluster cores. This structural change affects the (extreme) nonlinear optical properties of such white-light emitting materials, as shown by a combined experimental and quantum-chemical study.

We herein proposed and demonstrated a strategy of constructing the double-walled framework to target a highly porous and robust HOF material (ZJU-HOF-5a), exhibiting one of the highest gravimetric and volumetric surface areas for extraordinary high-pressure methane and hydrogen storage capacities.

In situ carburization of the Mo-based catalyst at 500 °C is achieved in RWGS reaction. The surface O/Mo atomic ratio plays significant role in carburization, i.e., lower surface O/Mo atomic ratio is beneficial to carburization. In situ carburization induced by reaction product of CO strongly promotes the RWGS activity showing CO formation rate of 7544.6 mmol ⋅ g_catal⁻¹ ⋅ h⁻¹.

For the first time, a bifunctional thiourea-amine-based organocatalyst has been employed in the ring-opening polymerization of optically active D- and L-methyl glycolide (MG) at room temperature. This innovative, metal-free catalytic approach leads to highly alternating poly(lactic-co-glycolic acids) (PLGAs), both in linear and star-shaped forms. The synthesized PLGAs exhibit high regioselectivity, consistent alternating structure, recyclability, and atactic microstructure, making them suitable for drug delivery applications.

A novel tetranuclear Cu(I) complex (Cu4) was developed based on apoferritin, which not only inhibited tumor growth through cuproptosis and cuproptosis-induced immunity, but also possessed significant CuAAC reaction to synthesize a chemotherapeutic resveratrol analogue in situ for achieving targeted dual-drug combination therapy for cancer.

We reported the detailed proton-driven dynamic behaviors of nanoconfined water between hydrophilic MXene sheets using molecular dynamics simulation based on the active learning potential trained by deep neural network algorithms. These findings have illuminated several novel phenomena including the MXene oxidation rate regulated by protons, the formation of a hexagonal ice phase exhibiting unconventional bonding patterns at room temperature, and a significant reduction in water diffusivity.

Taking advantage of the efficiency and substrate promiscuity of human ST6GalNAc enzymes along with a panel of enzyme modules, a library of human milk oligosaccharides (HMO) containing an atypical Neu5Aca2-6GlcNAc linkage including disialyllacto-N-tetraose (DSLNT) was synthesized for the first time. Glycan microarray assays revealed broad yet distinct recognition by Siglecs of the atypical Neu5Aca2-6GlcNAc motif.

Spin-state switching of a spin-crossover complex on Cu(111) induced by injection of tunneling electrons. The spin-state is readout from the low-voltage differential-conductance spectrum: the high-spin state exhibits magnetic excitation steps evolving with the application of a magnetic field while no spectroscopic feature is observed in the low-spin state.

A trace zwitterionic additive endows the Zn||Zn cells with a cycling life of more than 10000 hours. And the Zn||I₂ full cell exhibits 95 % capacity retention after 30000 cycles. Remarkably, the Zn||I₂ pouch cells (95 mAh) deliver a high-capacity retention of 99 % after 750 cycles.

An integrated molecular sieve@piperidine-decorated polyethylene separator is proposed for eliminating the H₂O-derived HF directly by an acid-base mechanism rather than the elimination of H₂O. This successfully enables LMBs with a LiF-rich SEI and stable cathode structure during cycling in an electrolyte with high H₂O content.

To identify the core region driving tauopathy, tau repeats within the microtubule-binding domain were synthesized and assessed for pathogenic traits. Repeat 3 initiated amyloid formation, cytotoxicity, and cognitive decline, with oligomeric aggregates showing pronounced neurotoxicity. This pathological form was utilized in a screening platform, leading to the discovery of tolcapone as a potent anti-tau agent. (SPPS=solid-phase peptide synthesis)

Extracting and obtaining lithium metal anodes from sea water for assembly of Li metal batteries by using single-channel Li ion-sieve membrane. The membrane effectively blocks water and interfering ions, allowing only Li ions to be transported.

In this work, XB adducts are formed between BzI-tethered amines and amines via the halogen bonding. After photofragmentation, the α-aminoalkyl radicals are generated and subsequently undergo radical addition to [1.1.1]propellane, yielding BCP radicals that participate in polarity-matched additions, culminating in the difunctionalization of bicyclopentane. The versatility of this approach is underscored by a series of valuable transformations.

Breaking upper limit of CO₂-uptake at low-pressure using porous materials is challenging due to the lack of multiple adsorption mechanisms. This study presents a novel concept of reversible multi-complexation of CO₂ to alkaline earth metal ion-pairs in ferrierite-type zeolite with the formation of unprecedented CO₂-complexes even at 400 ppm and 298 K. The findings in the present study offer a new direction for efficient CO₂ adsorbents.

Kaolin is demonstrated as an effective material to prepare Zn-based solid electrolyte (KL-Zn), which simultaneously eliminates the interfacial side reactions of zinc anode and inhibits the vanadium dissolution of NH₄V₄O₁₀ cathode, endowing high reversible capacity and superior cyclic stability for Zn//NH₄V₄O₁₀ batteries.

The N-doped carbon-coated Fe-based selenium oxide catalyst Fe₂O(SeO₃)₂/Fe₃C@NC was fabricated for zinc-air batteries (ZABs). The Fe−O−Se bonds in Fe₂O(SeO₃)₂/Fe₃C@NC@NC could obviously enhance catalytic performance of ORR and OER because it can modify coordination environment surrounding Fe atoms and accordingly realize an optimization of the adsorption energy of oxygen intermediates. Furthermore, the Fe₂O(SeO₃)₂/Fe₃C@NC-based ZABs exhibit superior peak power density and specific capacity in comparison to Pt/C+RuO₂-based ZABs.

Shewanella oneidensis MR-1 achieved months-long autotrophic growth and acetate production through CO₂ fixation coupled to sulfur oxidation, driven by biogenic CdS nanoparticles under light.

A facile synthetic method is developed to synthesize a large family of pyrazole molecule-protected borates containing cyclic eight-membered B₄O₄-ring as corns, in a rapid and precise manner under mild conditions. The obtained borates proved to be good electrocatalytic catalysts for CO₂ reduction reaction towards HCOOH and C₂H₄.

The reverse hydrogen spillover was mediated over operando stable Pd hydrides on tungsten carbides systems, which endows efficient and durable hydrogen evolution in proton exchange membrane electrolysis with ultralow Pd loading of 0.022 mg cm⁻².

Pathways from CO₂ to paraffin while from CO to C₂H₄ and C₃H₆ using Co−ZrO₂ photocatalyst were switched. CO₂ at the O vacancy on ZrO₂ transformed into COH and hopped onto Co⁰ to be paraffin while CO and H competed on Co⁰ leading to preferable coupling of CH₂ to olefins.

We obtained the activation enthalpies of graphene island growth on Cu(111) foils using H₂ and: CH₄, and C₂H₂, C₂H₄, and C₂H₆, respectively. The rate determining step (RDS) for CH₄ is its gas phase decomposition to H and CH₃. The RDS for C₂H₂, C₂H₄, and C₂H₆ is dehydrogenation on the Cu(111) surface yielding adsorbed C₂H₁, C₂H₃, and C₂H₅, respectively.

A β-cyclodextrin polymer is used to construct a quasi-single ion conductor for coating the Zn anodes, and thereby inhibited the corrosion of Zn anode, prevented the side reaction, elevated the Zn ion transference number, suppressed the formation of space charge regions and stabilized the plating/striping of Zn ions.

Novel NIR phosphors are constructed using a n-π-n molecular design strategy. Their phosphorescence can be readily modulated by altering the conjugated core structures. When incorporated into a 4-bromobenzophenone host, these materials exhibit efficient NIR phosphorescence ranging from 655–710 nm. Analysis of the exciton transition process reveals that the enhanced phosphorescence of the guest originates from the triplet energy transfer of abundant triplet excitons generated independently by the host material.

During the charging process of lithium cobalt oxide cathode, Li⁺ undergoes solvation, and Li⁺-complexes aggregate in the cathode-electrolyte interface, forming a concentrated interface. As the voltage increases, the intensified interfacial electric field exerts greater electro-repulsion on Li⁺, forming a diluted interface.

We report atomically dispersed manganese (Mn) embedded on nitrogen and sulfur co-doped graphene for ORR in alkaline electrolyte, realizing a half-wave potential (E_1/2) of 0.883 V vs. reversible hydrogen electrode (RHE) with negligible activity degradation after 40,000 cyclic voltammetry (CV) cycles. Introducing sulfur (S) changes the spin state of single Mn atom from high-spin to low-spin, optimizing the oxygen intermediates adsorption.

The development of an effective nickel-catalyzed carbonylative cross coupling of redox-activated alkyl carboxylic acids and aryl boronic acids is presented. A wide variety of alkyl aryl ketones is obtained in good yields, and the chemistry is easily applicable to stable and radiocarbon isotope labeling. The mechanism of the transformation has been investigated applying experimental and DFT methods.

The [SbCl₅]²⁻ luminescent center structure is formed by self-assembly of SbCl₃, methylamine hydrochloride, and 18-crown ether-6. This asymmetric structure can control the emission of singlet-triplet hybrid excitons by wavelength at room temperature. Under ultraviolet irradiation at 310 nm, it shows strong emission at 470 nm, white light emission under 340 nm irradiation, and strong emission at 570 nm under 370 nm irradiation.

A universal approach was developed to tune the selectivity of Cu-based catalysts in CORR from acetate to ethanol by tailoring the thermodynamic activity of water. The faradaic efficiencies of ethanol and alcohol can reach 42.5 % and 55.1 % at 700 mA cm⁻², respectively. The ability to control the selectivity of CORR opens up new possibilities for synthesizing a wider range of valuable chemical products from CO₂.

Novel sodium thiotellurate (Na₂TeS₃) interfaces are constructed both on the cathode and anode for Na−S batteries to simultaneously address the Na dendritic growth and polysulfide shuttling. Benefiting from this rational design, an anode-free cell fabricated with the Na₂S/Na₂Te@C cathode delivers an ultrahigh initial discharge capacity of 634 mAh g⁻¹ at 0.1 C under practically necessary conditions, which could pave a new path to design high-performance cathodes for anode-free RT Na−S batteries.

An unprecedented and efficient approach for the synthesis of multi-substituted anilines was reported. With a simple Mo-catalyst, a wide range of 2,4-di and 2,4,6-trisubstituted anilines, some of which were otherwise challenging to access, were efficiently prepared in generally good yields from readily accessible ynones and allylic amines. This process was robust, modular and ready for the syntheses of various valuable multi-substituted anilines.

The intrinsic molecular chiroptical properties (electronic circular dichroism and circular polarized luminescence) of helicences are perfectly transferred from solution to the crystal state and to water-soluble nanoparticles by encapsulating the chiral emitter in supramolecular small-molecule, ionic isolation lattices (SMILES). Furthermore, CPL brightness is enhanced by combination with a rhodamine antenna system.

A cascade Nazarov cyclization/dicycloexpansions reaction for the efficient synthesis angularly fused M/5/N tricyclic skeletons (M=5, 6; N=4–9, 13) has been explored. In this novel transformation, the priority of ring expansion could be predicted by the rational design of the ring size and substituents. Employing the reaction as a key step, we finished total synthesis of nominal madreporanone for the first time.

A nanoporous and chemically bonded S-Scheme heterojunction photocatalyst is synthesized by hybridization of two semiconducting MOFs, which exhibits excellent performance of photocatalytic nitrogen reduction reaction with an NH₃ production rate of 2.1 mmol g⁻¹ h⁻¹, an apparent quantum yield value of 16.2 % at 365 nm and a solar-to-chemical conversion efficiency of 0.28 %.

Inversely relationships between vacancy volume in vacancy-ordered double perovskite derivatives with their luminescent quantum yield and water stability have been established for the first time based on a series of [N(alkyl)₄]₂Sb□Cl₅□′-type vacancy-ordered perovskite derivatives.

New 0D hybrid Zn halide family with high water-resistance and simultaneous integration of cyan STE emission and ultralong green afterglow was firstly synthesized by skillfully manipulating metal halides and organic phosphors as independent optical centers. Through regulating heavy atom effect to control the intersystem crossing rate and spin-orbit coupling, the dormant emitting units were significantly activated resulting in unprecedented high emission efficiency for both STE and afterglow emissions in 0D hybrid metal halides, which was applied for color-time-dual-resolved anti-counterfeiting and information encryption-decryption.

Homochiral superhelical COF nanofibers were synthesized by manipulating the lengths of alkyl chains in enantiopure BINOL-based organic linkers. The resulting 3D chiral COFs formed right- and left-handed superhelix fibers with macroscopic chirality. These nanofibers exhibit significantly enhanced enantiodiscrimination in carbohydrate binding and a remarkable chirality-induced spin selectivity (CISS) effect.

A newly synthesized complex, KCB₉H₁₀ ⋅ 2C₃H₄N₂, with the dihydrogen bond structural features, exhibits a high ionic conductivity of 1.3×10⁻⁴ S cm⁻¹ at 30 °C, four orders of magnitude greater than that of KCB₉H₁₀ and the highest ionic conductivity reported to date for hydridoborate-based K⁺ conductors. This work offers a promising strategy for synthesizing solid K-ion conductors with enhanced conductivity.

A novel fullerene derivative (denoted as C₆₀-TMA) is synthesized and employed to modify the interface between perovskite and C₆₀. C₆₀-TMA can passivate the surface defects to suppress non-radiative recombination, form a cascade energy level to facilitate electron extraction, and induce secondary growth of perovskite, contributing to a champion PCE of 24.89 % for inverted PSCs with significantly improved thermal stability.

A comprehensive experimental investigation of the mechanistic aspects of the selective electroreduction of CO₂ to CO by an iron porphyrin using IR and UV/Visible absorption spectroelectrochemistry provides operando insights at molecular scale. In addition to the main catalytic cycle involving Fe^I species as resting state, a secondary pathway involving the protonation of the porphyrin ligand into a phlorin ligand at the Fe⁰ level was identified.

Under photoredox catalysis, novel heterocyclic sulfoximines serve as methyl and perdeuteromethyl radical sources. The reagents are bench-stable and easy-to-use. Various radical acceptors can be applied leading to products in good yields. Up-scaling has been achieved by using a photoflow reactor. Physicochemical studies suggest a photoredox process.

Fifteen imine-linked covalent organic frameworks were synthesized in hours in the same mixture of n-butanol, water and acetic acid while stirring. The method is convenient, green, tolerates a wide variety of monomers, and can produce over ten grams of covalent organic framework in one batch.

Fusions of protein-binding aptamers to the fluorescent light-up aptamer RhoBAST enabled visualization of GFP-tagged or endogenous proteins in both fixed and live mammalian cells. The fast exchange of the fluorogen yields intermittent fluorescence required for super-resolved imaging by RhoBAST-PAINT, a single-molecule localization technique.

Superchaotropic dodecaborate cluster anions adsorb efficiently on lipid mono- and bilayers, affecting the physical properties of the membrane more strongly than conventional chaotropic anions. Cluster immersion in the bilayer leads to a reorganization of the lipid chains, affording hybrid organic–inorganic membranes with expanded surface area per lipid as well as thinner membranes with increased fluidity.

Pronounced physisorption of bioactive cations with a hydrophobic alkyl chain by porous carbons with a negative zeta potential results in confined cations, which triggers anion enrichment and depletion under electric polarization and enables rapid differential ionic memresistance behavior for cations with strong and weak interactions with porous carbons.

The unexpected discovery of the photosensitization properties of 1-acetylpyrene for the thia-Paternò–Büchi reaction enabled the limitations of this hetero-cycloaddition reaction to be tackled in terms of substrate scope and efficiency. The synthesis of a wide range of thietanes from intrinsically unstable thiocarbonyls was made possible by the use of pyrenacyl sulfides as a source of both the thiocarbonyl substrate and the photocatalyst.

The Van-der-Waals distance of a thiol and ene is depicted. After the thiol-ene reaction a thioether bond is formed resulting in a shorter interatomic distance. This shrinkage leads to stress in the polymer which can be reduced by radical-mediated redox-rearrangements catalyzed by thiols. A compact cyclic acetal extent to a longer linear ester. This volumetric expansion is counteracting the shrinkage resulting from the thiol-ene reaction.

Calcium sulfate is a mineral of considerable relevance for various industrial and geochemical processes. In the present work, the formation of calcium sulfate dihydrate (gypsum) crystals from aqueous solutions has been elucidated in detail through application of a complementary suite of advanced characterization techniques. The results show how crystalline order emerges from intrinsically disordered precursors and highlights the complexity of mineral nucleation.

The biosynthesis of pyrrolizwilline produced by XhpA-G was elucidated in Xenorhabdus hominickii using a promoter exchange approach together with heterologous expression of xhpA-G in E. coli. We also report the structural characterization of XhpG, the key enzyme in the conversion of the intermediate pyrrolizixenamide to pyrrolizwilline.

We present a chaperone-derived Cu⁺-binding peptide featuring the conserved MTCGGC Cu⁺ binding motif, which self-assembles into nanofibers within cancer cells. These nanofibers have multiple MTCGGC Cu⁺-binding motifs on their surfaces, allowing for efficient capture of intracellular Cu⁺ ions. This process disrupts the Cu⁺ homeostasis network of cancer cells. Our study offers a novel therapeutic intervention targeting metal ion homeostasis in cancer.

Activating the strong H₂ bond is typically reserved for transition metals, and only a few main group systems can tackle this challenge. Here, we explore a phenyl radical mediated pathway utilizing the photolysis of iodobenzene. The phenyl radical leverages the high C−H bond energy of the forming benzene to drive H₂ activation. Low-temperature experiments and dual level instanton computations reveal hydrogen tunneling as a critical factor.

The synthesis of atomically precise Cu−Pd dimers within the nodes of a Cu-MOF was confirmed through detailed XAS experiments. DFT calculations suggest that the Pd atom in the Cu−Pd dimer modulates the binding energy of the key *COOH intermediate on the neighboring Cu site, leading to enhanced selectivity for electrocatalytic CO production during CO2 reduction.

We report first π-complexes derived from non-classical diboriranes (three-membered aromatic B₂C rings) and their carbonylative ring expansion to four- and five-membered cyclic ligands. The H-bridged diborirane (R=2,3,5,6-tetramethylphenyl; R’=H) initially reacts with Fe₂(CO)₉ to an allylic π-complex, which further reacts under side-on addition of CO to the B−B moiety to an η⁵-coordinated five-membered B₂C₂O ring. For R’=SnMe₃, CO is added end-on to the B−B bond.

Polymers with Ge=Ge double bonds in the σ,π-conjugational path are obtained via heavier acyclic diene metathesis of bis(digermene)s. High solubility and interchain dispersion interactions allow for near-infinite chains and deposition as thin films with ordered lamellar bundles. With the absorption in the visible range corresponding to small HOMO–LUMO gaps, this new class of conjugated materials is promising for various applications.

The van der Waals interfaces of graphene/MoS₂ heterostructures are tuned through controlled functionalization of the bottom graphene layer. Adjusting the size of the functional groups enables nm-scale modification of interlayer distances. Both the size and electronic properties of the functional groups are key to regulating charge transport, with size being particularly decisive.

We present a synthesis of cell-permeable NADs bearing fluorescent (TAMRA) or affinity (desthiobiotin) tag and their utility for ADP-ribosylation studies in living cells. Cell-permeability was achieved by modification with cholesterol or polyarginine. The probes were accepted by all tested PARP enzymes. The optimized desthiobiotin-labelled NAD⁺ was used for affinity enrichment and identification of proteins ADP-ribosylated upon oxidative stress.

Boroxine-based COFs including 3D COF-102 with high porosity, are now accessible by simple, efficient, and rapid mechanochemical synthesis, in a process amenable to in situ monitoring and multi-gram scale-up.

Spontaneous reactions of water in either highly charged nanodrops formed by electrospray ionization, or less highly charged microdroplets formed by a vibrating mesh screen nebulizer were investigated. No evidence for ionized water dimer, nor oxidation products of the radical scavengers caffeine or melatonin was observed over a wide range of droplet size, net charge, and lifetime, indicating that water is stable at the surface of unactivated water droplets.

A machine learning strategy utilizing crystal graph convolutional neural networks is proposed for the rational design of low-Pt high entropy intermetallic compounds (PtM₃ type, where M=transition metal) for the oxygen reduction reaction. The developed Pt(FeCoNiCu)₃/C catalyst, featuring small nanoparticle size, exhibits exceptional mass and specific activity, along with significantly enhanced electrochemical stability.

An automated electrochemical flow platform for operator-free data generation is presented, leveraging slug-based reaction mixtures for low material consumption. This platform was employed in the context of library synthesis of 44 medicinal chemistry-relevant compounds. The platform was also used to optimize one previously unsuccessful target via DoE, leading to a 6-fold yield increment.

We present a general system for the hydroboration of C−C single bonds without transition-metal catalysts. Our strategy surpasses the transition-metal systems regarding chemo- and regioselectivities, substrate scopes, or yields. Mechanistic studies, DFT, and IBO calculations revealed a hydroborane-promoted C−C bond cleavage and a hydride shift reaction pathway. The key role of the carbonyl group and the nitrogen atom of the amide was disclosed.

The first synthesis of the epidithiodiketopiperazine (−)-dithiosilvatin is reported along with a collective approach to ten related thiosilvatins. The described methods offer a practical blueprint for exploring the dithiotiketopiperazine pharmacophore with absolute and relative stereocontrol.

Lithium-based chemistries enables ferri/ferro-cyanide redox couple with high concentration of 0.8 M to access a broad range of physicochemical and electrochemical properties at −10 °C that represents the lowest operating temperature for ferri/ferro-cyanide catholyte reported so far.

Di-, tri-, and tetraacetoxysilanes reacted with silanols or silanediols under base- and catalyst-free conditions to selectively generate acetoxy-containing di- and trisiloxanes. Cyclotetrasiloxanes and bicyclic pentasiloxanes with precisely constructed structures were obtained from successive one-pot reactions of a tetraacetoxysilane with various silanediols. The acetoxy-containing oligosiloxanes can serve as efficient surface-treatment agents and as new building blocks for heat-resistant materials.

Spectroscopic evidence is presented for the binary, hypervalent [OF₃]⁻, formed in the reaction of OF₂ with laser ablated MF (M=Li−Cs) under matrix-isolation conditions. Quantum-chemical calculations show that the bonding in [OF₃]⁻ is similar to that in [F₃]⁻.

The addition of chiral sulfinimines to keteniminium ions generated through electrophilic amide activation enables a [3,3]-sigmatropic sulfonium rearrangement to yield enantioenriched β-ketoamides in a single step. The transformation proceeds with high enantio- and chemoselectivity as well as functional group tolerance, and—in contrast to imide-based chiral auxiliary approaches—directly delivers stereochemically stable amide products.

A T-shaped 11-electron chromium(I) complex was stabilized by a (PNP) ligand and fully characterized. An sp-sp carbon-carbon bond scission in dialkynes was found to occur at the vacant in-plane coordination site through the formation of a dinuclear dimer.