Exocytosis from beta cells monitored by amperometry is compared to the vesicle content assessed from intracellular vesicle impact cytometry to determine if partial release is dominant. Serotonin was used as an electroactive proxy for insulin as it is co‐released. The fraction of release from insulin‐containing granules in beta cells was found to be at most 34 %, providing a new perspective on insulin release for diabetes research.

Acyclic tertiary amines with alkyl substitution undergo two consecutive C(sp³)−H silylation reactions with dihydrosilanes to form 4‐silapiperidines. Bond formation occurs β to the nitrogen atom at two of the alkyl residues. The reaction is catalyzed by the strong boron Lewis acid B(C₆F₅)₃ and involves enamine intermediates generated by dehydrogenation.

The haem in bacterioferritins has been shown before to provide an electron to the ferritin's mineral core—to reduce Fe³⁺ to water soluble Fe²⁺. This work shows that the haem can also provide an electron, over a distance of approximately 13 Å, to the di‐iron ferroxidase centre of the protein, in a redox process not yet known.

Reported for the first time is an unusual borane‐initiated polymerization of arsonium ylide monomers, where the main‐chain grows by five carbon atoms, from the monomer, at a time and leads to unique structures.

The asymmetric synthesis of N‐substituted α‐amino esters has been achieved, in high yields and excellent enantioselectivities, employing sequence diverse metagenomic imine reductases (IREDs).

Complex solid solutions (“high‐entropy alloys”) promise a paradigm change in electrocatalysis but expose the challenge of almost unlimited options in adjusting their compositions. We propose the utilisation of computational models, combined with high‐throughput experimentation for the verification of the model assumptions, which allows for model refinement in iterative loops, understanding of binding mechanisms, and discovery of the most active composition.

A powerful alternative to the Nozaki‐Hiyama‐Kishi reaction serves as the key transformation in the total synthesis of chondrochloren A. Using a novel combination of the Hoppe anion in Matteson rearrangements serves to overcome the inherent synthetic challenges of the polyketide portion of chondrochloren A and paves the way to its total synthesis. Remarkably, this transformation can be performed stereoselectively in the absence of sparteine.

This contribution describes the observation of spin–electric coupling utilizing electric‐field‐modulated ESR (EFM‐ESR) spectroscopy for single‐crystals of a spin triangle which is characterized by the strong magnetic anisotropy of the individual cobalt(II) centers and a pronounced sensitivity of the molecular energy levels on the relative orientation of their magnetic axes as well as the exchange coupling between them.

A unique, highly incompressible fluid formed by a tight association of water molecules around ammonium and phosphonium salts is described in this paper. Applications of this new family of supramolecular fluids in different electrochemical processes are demonstrated in this work.

The characterization of η²‐N,N′‐N₂O and CO₂ complexes of nickel and the associated computational study reveal that the bonding ability of N₂O to nickel is intermediate between that of CO₂ and that of H₂C=CH₂. It is shown that in general, N₂O η²‐binds to metals comparably to or stronger than CO₂, indicating that the rarity of η²‐N₂O metal complexes is due mostly to its oxidizing character and not to its weak σ‐donating and π‐accepting properties.

The diborane(4) B₂(o‐tolyl)₄ reacts with species with B−H bonds giving a complex mixture arising from hydride/aryl exchange, dimerization and borane elimination. Use of BH₃ sources led to the isolation of the first tetra‐substituted pentaborane(9) HB[B(o‐tolyl)(μ‐H)]₄.

Extremely stable Blatter's type organic radicals grafted into the mesoporous silica show advanced relaxation properties at room temperature. Electron spin decoherence time exceeds that in many other qubit candidates, allowing efficient spin manipulation at ambient conditions. The tuneable multifunctional nature of such composite materials promotes them as promising nanoplatforms for developing new spin‐based quantum bits.

Targeting actin requires spatiotemporal control of drug activity. Optojasps are photo‐switchable small molecules, providing direct optical spatiotemporal control of the actin cytoskeleton. We present high‐resolution cryo‐EM structures of both isomeric states of an optojasp bound to F‐actin and describe in detail the binding pocket and conformational changes associated with switching of the azobenzene.

A Ni‐deposited carbon nitride material was developed as a fully heterogeneous dual photocatalyst. Visible light‐driven C–O cross‐coupling is demonstrated free of organic ligands and additives. This dual catalytic system operates with very low nickel loadings and the heterogeneous photocatalyst can be easily recycled.

DNA origami platforms were used to assemble synthetic supramolecular polymers, retaining their dynamic nature with control over monomer composition and loading and dynamic exchange of molecular cargo. The DNA origami‐templated self‐assembly allows for novel strategies for controlled multicomponent self‐assembly and characterization of synthetic supramolecular systems.

A fluorescence‐based competitive assay was developed, which enabled the high‐throughput screening of various cyclic peptides targeting the Lys48‐linked tetraubiquitin chain. This assay combined with chemical tools enabled the design of a potent dimeric cyclic peptide, which induced cell death with higher efficiency compared to its monocyclic analogue.

A CO₂, pH, and thermo‐responsive emulsion was developed to perform multienzyme cascades without incompatibility and cross‐reactivity issues. This emulsion allows the on‐demand control of morphology and phase composition, and therefore exchanging enzymes and separate yielding/recycling of products and polymers. A three‐enzyme cascade was performed sequentially, each step was carried out under the optimal conditions of the corresponding enzyme.

Twelve sugars, differing in size and stereochemistry, were used as building blocks in a modular, efficient four‐step synthetic route to multifunctional BODIPY glycoconjugates with high fluorescence and hydrophilicity. The chiral information was transferred unchanged, thereby providing complex and distinct probes for target‐oriented binding studies and specific in vivo imaging.

Phosphazene organocatalysts have been found to promote a highly‐active, controlled, and selective alternating ring‐opening copolymerization of N‐sulfonyl aziridines and cyclic anhydrides. This one‐pot methodology leads not only to homopolymers but also to poly(ester amide)‐based block copolymers.

Two pathways are proposed for the synthesis of an important class of functionalized phthalocyanine‐porphyrin hybrids (TBTAPs). The materials are novel in their own right, but more importantly, the syntheses offer control and variation over structural and substituent modifications, a goal not yet achieved even within the extensively investigated chemistry of the parent phthalocyanines.

Divergent radical sp³ C−H functionalization of N‐alkyl anilines has been achieved using a photoredox strategy. This approach enables to overcome back‐electron transfer and therefore allows direct access to previously elusive α‐anilinoalkyl radicals.

A radically new approach to the synthesis of 1‐(dialkylamino)‐1,2,3‐triazoles via addition of diazomethyl radicals to hydrazones is described. This reactivity confirms the utility of the α‐diazosulfonium salts herein introduced as synthetic equivalents of the diazomethyl cation.

The scope of carbon–carbon bond‐forming hydrogen‐borrowing reactions has been expanded to include 1,2‐amino alcohols derived from both natural and unnatural amino acids. The vulnerable amine stereocentre is preserved in the reaction by the use of a bulky nitrogen protecting group (trityl or benzyl), with the products being readily cleaved under acidic conditions to the corresponding γ‐aminobutyric acids without further purification.

Green or blue? The wavelength controls the outcome. Chromoselective activation of a carbon nitride generates electron holes with different oxidation potentials that are used for selective oxidation processes. By coupling the photocatalytic reactions with biocatalysis the (S)‐ or the (R)‐enantiomer of 1‐phenylethanol was synthesized stereoselectively.

We describe a chemical strategy to prepare sucrose derivatives with vibrational tags and the characterisation of the first optical analogue of sucrose able to image real‐time trafficking of sucrose in live plant cells.

An iodine‐assisted method has been developed for etching bulk Ti₃AlC₂ in anhydrous acetonitrile (CH₃CN), resulting in 2D MXene sheets (Ti₃C₂T_x, T=O, OH) with intact lattice, high yield (71 %), large size (1.8 μm) and ultimate thickness (<5 nm). 2D MXene sheets present great ambient stability in water for at least 2 weeks and high gravimetric capacitances of 293 F g⁻¹ at 1 mV s⁻¹ when serving as electrode materials for supercapacitors.

Metal‐free diazotransfer on native RNA using the reagent FSO₂N₃ selectively provides azide‐modified RNA in quantitative yields. The stereochemically controlled reaction opens new avenues for the synthesis of RNA‐peptide conjugates and for the isolation of cellular RNA containing post‐transcriptional nucleotide modifications with an aliphatic primary amino group, such as acp³U.

A novel catalytic system based on copper(I) and chiral bis(phosphine) dioxides is described. This allows the arylation of silyl enol ethers to access enolizable α-arylated ketones in good yields and enantiomeric excess up to 95%. Noncyclic ketones are amenable substrates with this method, which complements other approaches based on palladium catalysis. Optimization of the ligand structure is accomplished via rational design driven by correlation analysis. Preliminary mechanistic hypotheses are also evaluated in order to identify the role of chiral bis(phosphine) dioxides.

The separation of styrene (ST) and ethylbenzene (EB) mixtures is of great importance in the petrochemical and plastics industries. Current technology employs multiple cycles of energy-intensive distillation due to the very close boiling points of ST and EB. Here, we show that the molecular sieving properties of easily scalable and stable trianglimine crystals offer ultrahigh selectivity (99%) for styrene separation. The unique molecular sieving properties of trianglimine crystals are corroborated by DFT calculations, suggesting that the incorporation of the nonplanar EB requires a significant deformation of the macrocyclic cavity whereas the planar ST can be easily accommodated in the cavity.

We report here a scalable, catalytic one-pot approach to enantiopure and unmodified β²-amino acids. A newly developed confined imidodiphosphorimidate (IDPi) catalyzes a broadly applicable reaction of diverse bis-silyl ketene acetals with a silylated aminomethyl ether, followed by hydrolytic workup, to give free β²-amino acids in high yields, purity, and enantioselectivity. Importantly, both aromatic and aliphatic β²-amino acids can be obtained using this method. Mechanistic studies are consistent with the aminomethylation to proceed via silylium-based asymmetric counteranion-directed catalysis (Si-ACDC) and a transition state to explain the enantioselectivity is suggested on the basis of density functional theory calculation.

Unexpected conformational changes involving a global concerted rearrangement of the structure have been evidenced in large multistranded aromatic sheets. Increasing foldamer size thus gives access to new and defined conformational trajectories.

Using VCD spectroscopy as key analytical tool, it was found that point chirality in side chains of chiral triarylborane–ammonia adducts, which feature intramolecular hydrogen bonds in addition to the dative N→B bond, can efficiently be transferred to triarylborane propeller chirality.

Cyclic (alkyl)(amino)carbene (CAAC) precursor salt 2BF₄ reacts with [M(PPh₃)₄] (M=Pd, Pt) to give cis/trans‐[3]BF₄ and cis‐[4]BF₄, in which the CAAC ligand bears an unusual N‐alkyl substituent. trans‐[5] has a unique anionic CAAC ligand with an unsubstituted ring‐nitrogen atom which can be protonated to give trans‐[6]BF₄ bearing a protic CAAC (pCAAC) ligand.

An efficient, racemic, and enantioselective total synthesis of the diterpene waihoensene is presented. Key steps are a radical cyclization, a Pauson–Khand reaction, and an asymmetric allylic decarboxylative allylation (AAA) reaction to obtain optical active material.

α‐C−H arylation of N‐alkylamides using 2‐iodoarylsulfonyl radical translocating arylating (RTA) groups is reported. The RTA group fulfills multiple roles: It acts as radical precursor, engages in remote C−H activation via hydrogen atom transfer, and serves as arylating moiety. The method allows the construction of α‐quaternary carbon centers in amides and shows broad substrate scope.

Br‐NHC‐Au^I complexes were designed as starting points of Kumada polymerizations to grow regioregular poly(3‐hexylthiophene)s‐NHC‐Au^I, which were reduced to afford P3HT‐NHC@Au NPs. In addition to excellent thermal as well as redox stability, the corresponding NPs show improved charge transfer behavior due to the effective electron delocalization over the gold/P3HT interface benefiting from the robust and conductive NHC linkages.

Biogenesis of amyloid‐β peptides from their precursor protein can be tracked in endocytic compartments of living cells by a molecular beacon labeling strategy based on genetic code expansion.

A SEM‐controlled micromanipulator technique is proposed to pick single Co₃O₄ nanoparticles and place them on a modified carbon nanoelectrode surface. The obtained nanoassembly allows to extract the intrinsic oxygen evolution activity of the nanoparticle at industrially relevant current density devoid of film and ensemble effects. Post‐electrochemistry TEM analyses offer insight into structural transformations during electrocatalysis.

Here, a non‐equilibrium state of interaction between supramolecular lipopolysaccharide (LPS) and Aβ42, an aggregate‐prone protein that causes Alzheimer's disease (AD), was identified. Oscillation of the non‐equilibrium state for co‐assembly and clearance of Aβ42 is triggered through the use of a supramolecular bait. Since the impaired clearance of toxic Aβ42 deposits correlates with AD pathology, the LPS and Aβ42 non‐equilibrium could represent a useful target for developing AD therapeutics.

A plausible scenario for the prebiotic generation of activated RNA substrates under mild aqueous conditions is presented. Using water‐soluble diamidophosphate, in situ production of 2′,3′‐cyclic phosphate‐activated oligoribonucleotides and their subsequent ligation by a ribozyme can be achieved.

The electronic nature of Sb‐ and Bi‐doped lead halide perovskites is an area of current scientific debate. Model compounds featuring [PbE₂I₁₆]⁸⁻ (E=Sb, Bi) anions that represent precise cut‐outs of doped perovskites are presented. The compounds display surprisingly low band gaps owing to an excellent electronic match between PbI₆ and EI₆ units and represent the first members of a promising new class of metal halide materials.

A stable cyclic diaminosilylene featuring a ferrocene‐based backbone is reported. The dicoordinate Si^II atom is part of a six‐membered FeC₂N₂Si ring and shows a comparatively large bond angle of ca. 107°. This N‐heterocyclic silylene can activate strong bonds (C=O, N=O, B−H, N−H, P−H, O−H) under ambient conditions.

Dimerization of linear butenes and pentenes at zeolitic Brønsted acid sites yields, rather than branched alkenes, alkanes featuring a cyclohexane ring. The absence of any C=C double bond in the latter explains not only the observed change of the IR spectra, but also the observation that oligomerization stops at the dimer.

The effect of thermal vibrations on anisotropic NMR parameters, such as residual dipolar couplings (RDCs), is evaluated. It is shown that this “structural noise” significantly affects the certainty with which relative configurations of chiral compounds can be assigned by using RDCs.

The one‐electron reduction of a cyclic (alkyl)(amino)carbene (CAAC)‐stabilized borylene carbonyl complex yields a dimeric borylketyl radical anion, resulting from an intramolecular aryl migration to the CO carbon atom. Computational analyses support the existence of a [(CAAC)B(CO)Ar]^.− radical anion intermediate. Further reduction leads to a highly nucleophilic dianionic (boraneylidene)methanolate.

A highly contorted π‐expanded polycyclic tetra‐anion comprising a cyclooctatetraene moiety is readily formed upon reduction of the neutral precursor with lithium metal. The highly charged carbanion crystallizes with four lithium counterions, two of which stabilize the contorted structure through internal coordination. Density‐functional theory calculations rationalize the unexpected formation of the tetra‐anion and provide insights into its electronic properties.

Super‐iMICs (5) with the largest buried volume (V _bur=45 %) known thus far for iMICs are accessible via unprecedented Ni‐catalyzed intramolecular 1,2‐aryl migration of C5‐protonated iMICs (2) to 3, subsequent N‐alkylation of 3 to 4, and the deprotonation of 4. S‐iMICs (5) are stronger σ‐donors and superior π‐acceptors than 2. A comparative catalytic study reveals superior activity of S‐iMICs (5) over iMICs (2) and NHC (IPr).

Dehydroamino‐acid‐containing natural peptides and proteins were rapidly and selectively borylated at the β‐position using copper(II) catalysis. The introduced boronic‐acid functionalities are valuable handles for chemical mutagenesis and, in a reversible click reaction with triols, for the pH‐controlled labeling of ribosomally synthesized and post‐translationally modified peptides (RiPPs).

Azetidines can be enantioselectively prepared from the title compounds and various 1‐arylethenes. An intramolecular variant of the reaction is also possible, and the lactam ring of the products 1 can be readily cleaved without loss of enantiopurity.

For the first time, the 3c–4e bond of a symmetric trichlorine anion [Cl]⁻ was characterized by experimental charge density investigations and compared to two asymmetric cases. Quantum‐chemical DFT calculations for both periodic crystals and isolated molecules/ions flank those studies. There appears to be a smooth transition from the asymmetric to the symmetric compound.

The Ga=E double bond in gallapnictenes LGaEGa(Cl)L (E=As, Sb) serves both as electrophilic and nucleophilic center, whereas the corresponding pnictanide anions [L(Cl)Ga]₂E⁻ are strong nucleophiles.

The β‐H elimination event that brings about chain transfer and branch formation in neutral nickel‐catalyzed olefin insertion polymerization is now fully addressed by a C _s‐type shielding of both apical positions of a neutral Ni^II catalyst. Thus, strictly linear (<0.1 brs/1000C) ultrahigh molecular weight polyethylenes (UHMWPEs; 5050 kDa) are now accessible.

An enantioselective electronic nose based on an array of six sensors coated with nanoporous metal–organic framework films of different homochiral and achiral structures is presented. Each chiral film shows a different response for each enantiomer of the chiral odor molecules, allowing their discrimination. All tested odor molecules can be enantioselectively identified with high precision by using the combined data of the sensor array.

Upon reaction of silylated [Ge₉] clusters with 1,3,2‐diazaborolidines boranyl‐functionalization is achieved. The presented experiments aim for the generation of frustrated Lewis acid–base pairs as predicted from quantum‐chemical calculations.

A heteroleptic silyl supported stannylene enables activation of white phosphorus and use as P‐atom transfer reagent.

Understanding reaction mechanisms is crucial to knowledge‐driven catalyst design. Here, NMR spectroscopy and DFT are combined to unravel the mechanism of “CO‐free” hydroesterifications. Methyl formate is found to be the key intermediate in this Pd‐catalyzed reaction. This is supported by the first observation of a Pd‐formyl species.

A novel one‐pot synthetic strategy towards a series of boron‐doped polycyclic aromatic hydrocarbons from ortho‐aryl substituted diarylalkynes has been developed. A reaction mechanism is proposed based on the experimental investigation together with the theoretical calculations, which involves an unprecedented 1,4‐boron migration process.

A molecularly imprinted polymer (MIP) based smart prodrug delivery nanoplatform was demonstrated with the ability to specifically target tumor sites with prolonged retention time and gradual tumor microenvironmental pH‐triggered release. The MIP‐based prodrug delivery is liver‐independent but tumor‐dependent, which not only greatly enhances tumor specificity but also expands the scope of applicable prodrugs.

The synthesis of a carbenaporphyrin ligand based on carbazole and triazolylidene is reported. Instead of a macrocyclic aromatic or antiaromatic character, the aromaticity of each heterocyclic moiety is preserved, which results in optical properties different from porphyrins, for example, fluorescence. In Li⁺ and Sc³⁺ complexes the ligand reveals striking geometric similarity to porphyrins, but is a stronger electron donor.

Irradiation of N‐acryloyl heterocycles with blue LED light and an Ir^III complex leads to fused γ‐lactam formation. The reaction proceeds via cyclization in the triplet excited state to yield a 1,4‐diradical; intersystem crossing leads to a singlet zwitterion that is geometrically restricted from yielding a cyclobutane. Proton transfer leads to the products in an interrupted [2+2] cycloaddition.

A photobioelectrochemical tandem cell is presented in which two photoelectrodes have been functionally coupled with two biocatalysts for supplying the light‐driven reaction with charge carriers from glucose conversion. The cell allows the generation of electricity from biofuels and light with a high open‐circuit voltage of 1 V.

Knight‐shift T ₂‐weighted MRI measurements of dendrite formation in all‐solid‐state batteries show direct contrast between the bulk electrode and the dendrite formation. This significantly increased T ₂ of the spalling dendrite formation is attributed to a local motion of the metallic Na ions.

In a series of experiments and by a theoretical analysis we decipher Raman optical activity induced in achiral solvents as an interference of two phenomena, circular dichroism and polarized Raman scattering. Applications of this strong effect can be potentially found in analytical chemistry, spectroscopy, and imaging of biologically relevant systems.

Amide metathesis is exploited as a route to boryl compounds of K, Ca, and Sr. The dimeric potassium system is shown by crystallographic and atoms‐in‐molecules studies to approach a limiting description as a “free” boryl anion.

Promiscuous acyltransferase activity is widespread in family VIII carboxylesterases. A detailed structure–function analysis improved understanding of this remarkable phenomenon and enabled us to rationally transform a hydrolase into an acyltransferase by introducing a single mutation.

A unique angle: A new approach for monitoring the real‐time permeation of drug molecules, from the bulk phase, across a lipid membrane was established by supporting a lipid bilayer on mesoporous silica thin films. Through the use of TIRF microscopy, the angle of incidence of illumination light could be controlled to ensure the resulting evanescence was restricted within the thin film, and thus, only drug permeating the bilayer was resolved.

Low‐oxidation‐state main‐group compounds exhibit rich oxidative addition chemistry. The same is not true for the reverse process, reductive elimination. Put together, the processes enable numerous catalytic cycles in transition‐metal chemistry. Here, using a stereoactive ligand as a reporter, it is revealed that Al^II dihydrodialanes exhibit transition‐metal‐like reversible reductive elimination. Mes=2,4,6‐trimethylphenyl.

A vanillin‐based 2‐methoxyhydroquinone is proposed as the catholyte for redox‐flow batteries. We overcame the tendency of such quinones to form reactive radicals that trigger side‐reactions by carefully choosing the medium. This enabled 87.4 % capacity retention after 250 cycles.

Here we describe the formation of an unexpected and unique family of hollow six-stranded helicates. The formation of these structures depends on the coordinative flexibility of silver and the 2-formyl-1,8-napthyridine subcomponent. Crystal structures show that these assemblies are held together by Ag₄I, Ag₄Br, or Ag₆(SO₄)₂ clusters, where the templating anion plays an integral structure-defining role. Prior to the addition of the anionic template, no six-stranded helicate was observed to form, with the system instead consisting of a dynamic mixture of triple helicate and tetrahedron. Six-stranded helicate formation was highly sensitive to the structure of the ligand, with minor modifications inhibiting its formation. This work provides an unusual example of mutual stabilization between metal clusters and a self-assembled metal–organic cage. The selective preparation of this anisotropic host demonstrates new modes of guiding selective self-assembly using silver(I), whose many stable coordination geometries render design difficult.

We report engineering of a P450 monooxygenase for the stereo‐ and regioselective 7β‐hydroxylation of lithocholic acid to produce ursodeoxycholic acid (UDCA). Structural and 3DM analysis, and molecular docking, identified selectivity‐influencing residues. A “small but smart” mutant library was then screened with a selective colorimetric assay. The best mutant has nearly perfect regio‐ and stereoselectivity, enabling a new route for UDCA synthesis.

2D CPs via the Horner–Wadsworth–Emmons Reaction: A novel methodology for the solvothermal bottom‐up synthesis of 2D vinylene‐linked conjugated polymers (2D CPs) with a nitrogen‐doped skeleton by linking hexaazatrinaphthalene (HATN) units and phenyl/biphenyl units by vinylene linkages is reported.

Active tau recruits tubulin into liquid‐like condensates and promotes microtubule assembly. Upon phosphorylation at the disease‐associated AT180‐epitope intramolecular salt bridges are formed and the microtubule‐assembly activity is lost.

A short 6‐step enantioselective synthesis of (−)‐finerenone is reported featuring a partial transfer hydrogenation of a naphthyridine ring. The naphthyridine existed in two atropisomeric forms that reacted at different rates and selectivities; however, at elevated temperature kinetic dynamic resolution occurred, enabling (−)‐finerenone to be obtained with high enantioselectivity.

Selective excitation of overlapped multiplets in a single scan broadens the applicability of 1D selective NMR experiments.

A modified implementation of DNA‐PAINT microscopy is used to detect spatial proximity of biomolecules with super‐resolution capabilities. The new technique, called Proximity‐PAINT, features a precisely tunable detection range, high sensitivity and low false‐positive rates. The implementation can be applied to visualize cellular protein‐protein interactions and other biomolecules of interest, such as nucleic acids.

Simple ethylene‐bridged oligo‐BODIPY precursors of various sizes serve as ideal substrates to undergo a one‐pot, multistep oxidation sequence with FeCl₃ to furnish benzene‐fused counterparts as fully conjugated, semicircular, near‐infrared dyes with interesting reduction behavior and high air stability.

The first heteronuclear vinyl anion consisting of two heavier Group 14 elements, silagermenide 3⋅K(18‐c‐6), is readily accessible by KC₈ reduction of a NHC‐stabilized germylene or the corresponding NHC‐free digermene. Its applicability as synthon for the synthesis of unprecedented functional silagermenes 4 a,b and evidence for significant π‐conjugation between the N=C and Si=Ge are also reported.

This work reveals the mechanism of atomic permeation through a subnano‐pore in graphenic lattice by in situ aberration‐corrected high‐resolution transmission electron microscopy imaging, highlighting the importance of chemical bonding between the mobile atom and dangling bonds around the subnano‐pore. This new phenomenon and permeation mechanism are likely to play a role in the filtration processes by porous graphenic carbon based membranes.

Proteins are genetically engineered and equipped with long supercharged polypeptide handles, rendering them susceptible to ultrasound. The concept is demonstrated by designing ultrasound‐responsive GFP derivatives the fluorescence of which can be switched “off,” while the activation of catalytic activity is switched “on” by ultrasound using trypsin in conjunction with a protein inhibitor.

Biocatalytic alkylations are valuable for late‐stage functionalization but are limited by the availability of S‐adenosyl‐l‐methionine analogs. Directed evolution was used to create an engineered halide methyltransferase capable of converting cheap and readily available alkyl iodides into a number of SAM analogs. Used in cascades with methyltransferases, this enables chemo‐, regio‐ and stereoselective alkylations which are difficult to achieve by chemical means.

The amplification of circularly polarised (CP) luminescence of a small chiral molecule embedded within an achiral polymer matrix is demonstrated. This amplification (from |g _PL|=0.0003 to 0.15) is observed in several achiral polymer hosts, due to electrodynamic coupling between the electric and magnetic transition dipoles of the donor (polymer) and acceptor (small molecule), which results in efficient CP Förster resonance energy transfer.

The combination of a chiral copper catalyst and a bifunctional ruthenium pincer complex enables the nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols. The enantioselective Cu‐H‐catalyzed dehydrogenative Si‐O coupling and the rapid transition‐metal‐catalyzed alcohol racemization are perfectly orthogonal. By this, high yields and good levels of enantioselection are achieved.

Is the latest addition to the periodic table an actual or a formal noble gas? Two complementary state‐of‐the‐art approaches reveal in unison that Og is a solid at ambient conditions. And with predicted melting and boiling points of 325±15 K and 450±10 K, not even particularly volatile.

Tantalum carbide dihydride cations are identified as products in the reaction of methane with gas‐phase Ta₄ ⁺ clusters by IR spectroscopy, in conjunction with density‐functional theory calculations.

Gallium(I) triflate is a promising new source of low‐valent gallium for synthesis and catalysis. However, little is known about its composition and structural chemistry. Here it is demonstrated that speciation is quite complex in this system, with compounds containing Ga in multiple oxidation states being isolated from arene solutions.

Arynes generated in situ are shown to be good acceptors for the persistent TEMPO radical. The adduct aryl radicals engage in typical radical reactions such as direct TEMPO trapping, cyclization, or hydrogen atom transfer. Final TEMPO trapping provides bisalkoxyamines. Cyclizations, dihydrobenzofurans, oxindoles, and sultones can be prepared by this conceptually novel aryne chemistry, nicely complementing existing aryne methodology.

Using the bimetallic combination sBu₂Mg⋅2 LiOR (R=2‐ethylhexyl) in toluene enables a very fast regioselective Br/Mg exchange of dibromo(hetero)arenes in toluene. The regioselectivity of the exchange can be finely tuned by the coordination preference of lithium, which can be switched, in some cases, by the addition of Lewis donors such as PMDTA.

Biomineralization occurs in aqueous environments. Despite the ubiquity and relevance of CaCO₃ biomineralization, the role of water in the biomineralization process has remained elusive. Here, we demonstrate that water reorganization accompanies CaCO₃ biomineralization for sea urchin spine generation in a model system. Using surface-specific vibrational spectroscopy, we probe the water at the interface of the spine-associated protein during CaCO₃ mineralization. Our results show that, while the protein structure remains unchanged, the structure of interfacial water is perturbed differently in the presence of both Ca²⁺ and CO₃^2– compared to the addition of only Ca²⁺. This difference is attributed to the condensation of prenucleation mineral species. Our findings are consistent with a nonclassical mineralization pathway for sea urchin spine generation and highlight the importance of protein hydration in biomineralization.

A new in situ nano‐spectroscopy technique elucidating the guest–host chemistry between Metal‐Organic Frameworks (MOFs) and water vapor is described. By using adapted Photoinduced Force Microscopy (PiFM) on amphiphilic surfaces of mixed HKUST‐1/ZIF‐8 films, site‐specific D₂O gas sorption isotherms could be determined. Furthermore, using in situ PiFM, the real‐time evolution of defective HKUST‐1 paddlewheels on the surface could be visualized.

The first tectosilicate‐analogous oxonium–bismuth borosulfate obtained from the reaction of oleum with bismuth nitrate and boric acid decomposes to the first bismuth borosulfate—a ring‐silicate‐analogous one—delivering exciting insights in the chemistry and the crystal structures of this still expanding material class.

Boron–nitrogen compounds have many applications in materials chemistry, hydrogen storage and medicinal chemistry. We report herein a new method for the construction of B−N bonds via the efficient and uncatalysed hydroamination of boron−boron multiple bonds with primary amines. The new diborenes generated are diboron analogues of enamines.

Only one very bulky substituent R is required to stabilize the first stable heteroindanediyls (see picture), which represent a group of resonance‐stabilized phosphorus‐centered biradicals. Different types of oligomers formed by self‐activation of the aromatic backbone were observed for smaller substituents.

Willing to interact are the tellurium and nitrogen atoms of Me₂N(CH₂)₃Te(C₆F₅) as was experimentally proven both in the solid state and the gas phase.

Designed with the correct pK _a value and appropriate electron withdrawing and pushing groups, benzoic acid and benzamidine are bioisosteric with respect to the binding to the hinge region of a kinase.

Conventional chemical bonding analysis distinguishes between two situations: electron sharing and donor‐acceptor. However, a third scenario is possible where the bond suffers spin polarization. Discussed here is the case of NaBH₃ ⁻, better classified as a spin‐polarized bond. A simple model to distinguish between these bonding types is provided.

An oxidative domino reaction is developed here for the construction of alkyne‐substituted cyclopentenol compounds by using an amino‐supported Pd catalyst. The properties of the heterogeneous catalyst contribute to its high efficiency and excellent chemoselectivity, as well as good recyclability.

A new diterpene synthase (CaCS) from Catenulispora acidiphila and its products were identified. The enzyme mechanism was studied by isotopic labelling experiments and usage of substrate analogues with blocked reactivity, resulting in a series of derailment products. Their chemistry was studied, leading to the biomimetic synthesis of a diterpenoid analogue of a brominated sesquiterpene known from the red seaweed Laurencia microcaldia.

Modular β‐borylacrylates are validated as programmable, ambiphilic C₃‐synthons for the annulation of 2‐halo‐phenol derivatives to generate diverse coumarins. Key to this [3+3] disconnection is the BPin unit which serves a dual purpose as both a traceless linker for C(sp²)–C(sp²) coupling, and as a chromophore extension to enable E → Z alkene isomerisation. Inverting alkene geometry is a pre‐condition to access 3‐susbtituted derivatives. This approach capitalises upon the abundance of 2‐halophenols in biology and may facilitate natural product/drug re‐purposing and the development of imaging tools.

A method for the direct C−H alkynylation of thiophenes has been developed. Complementary sets of reaction conditions enable a regiodivergence for 3‐substituted substrates, giving selective access to either the C2 or the C5 alkynylation products. The method works for various substitution patterns on the thiophene, features a broad scope, and uses the thiophene as the limiting reagent, rendering it suitable for late‐stage modification.

The photofunctionality of the cobalt–hexacarbene complex [Co(III)(PhB(MeIm)₃)₂]⁺ (PhB(MeIm)₃ = tris(3-methylimidazolin-2-ylidene)(phenyl)borate) has been investigated by time-resolved optical spectroscopy. The complex displays a weak (Φ ∼ 10^–4) but remarkably long-lived (τ ∼ 1 μs) orange photoluminescence at 690 nm in solution at room temperature following excitation with wavelengths shorter than 350 nm. The strongly red-shifted emission is assigned from the spectroscopic evidence and quantum chemical calculations as a rare case of luminescence from a metal-centered state in a 3d⁶ complex. Singlet oxygen quenching supports the assignment of the emitting state as a triplet metal-centered state and underlines its capability of driving excitation energy transfer processes.

An all‐organic core–shell colloidal catalyst was synthesized through two‐step surfactant‐free emulsion polymerization. The acid/base colloidal catalyst shows high catalytic activity in water, can be scaled up and recycled, indicating its potential for practical applications.

The yet underdeveloped coordination chemistry of Ga^I species won a new addition to their family. With an unprecedented bonding situation in main‐group chemistry, the complex salt Ga(COD)₂ ⁺[Al(OR^F)₄]⁻ (COD=1,5‐cyclooctadiene; R^F=C(CF₃)₃) offers novel options. Its properties are compared with respect to those of related transition‐metal species.

In recent years, several organocatalytic asymmetric hydroarylations of activated, electron-poor olefins with activated, electron-rich arenes have been described. In contrast, only a few approaches that can handle unactivated, electronically neutral olefins have been reported and invariably require transition metal catalysts. Here we show how an efficient and highly enantioselective catalytic asymmetric intramolecular hydroarylation of aliphatic and aromatic olefins with indoles can be realized using strong and confined IDPi Brønsted acid catalysts. This unprecedented transformation is enabled by tertiary carbocation formation and establishes quaternary stereogenic centers in excellent enantioselectivity and with a broad substrate scope that includes an aliphatic iodide, an azide, and an alkyl boronate, which can be further elaborated into bioactive molecules.

Sodium in Flow: A sodiation of substituted acrylonitriles and alkenyl sulfides with NaDA or NaTMP⋅TMEDA was performed using a commercial continuous flow set‐up leading to the corresponding organosodiums. Trapping with various electrophiles afforded functionalized acrylonitriles and alkenyl sulfides. This flow‐procedure was successfully extended to other acrylates by using Barbier‐type conditions.

Staple it! A terminal helical turn in heterodimeric coiled coils was stapled with a covalent lactam or a reversible metal‐coordination bond. The staples provide resistance to helix uncoiling and increase coiled coil stability to thermal denaturation and external mechanical forces.

Direct hydrogenation of thioesters with H₂ provides a facile and waste-free method to access alcohols and thiols. However, no report of this reaction is documented, possibly because of the incompatibility of the generated thiol with typical hydrogenation catalysts. Here, we report an efficient and selective hydrogenation of thioesters. The reaction is catalyzed by an acridine-based ruthenium complex without additives. Various thioesters were fully hydrogenated to the corresponding alcohols and thiols with excellent tolerance for amide, ester, and carboxylic acid groups. Thiocarbamates and thioamides also undergo hydrogenation under similar conditions, substantially extending the application of hydrogenation of organosulfur compounds.