Search

Halide perovskite quantum dots (PQDs) are promising materials for diverse applications including displays, light‐emitting diodes, and solar cells due to their intriguing properties such as tunable bandgap, high photoluminescence quantum yield, high absorbance, and narrow emission peaks. Despite the prosperous achievements over the past several years, PQDs face severe challenges in terms of stability under different circumstances. Currently, researchers have overcome part of the stability problem, making PQDs sustainable in water, oxygen, and polar solvents for long‐term use. However, halide PQDs are easily degraded under continuous irradiation, which significantly limits their potential for conventional applications. In this study, an oleic acid/oleylamine (traditional surface ligands)‐free method to fabricate perovskite quantum dot papers (PQDP) is developed by adding cellulose nanocrystals as long‐chain binding ligands that stabilize the PQD structure. As a result, the relative photoluminescence intensity of PQDP remains over ≈90% under continuous ultraviolet (UV, 16 W) irradiation for 2 months, showing negligible photodegradation. This proposed method paves the way for the fabrication of ultrastable PQDs and the future development of related applications., Solid‐state perovskite quantum dot papers are fabricated using a unique vacuum filtration growth method without a purification process. The bonding between cellulose nanocrystals and perovskite quantum dots makes the hybrid structure stable, and record high UV stability and thermal stability are achieved for perovskite quantum dot papers.

A novel paper‐based biofuel cell with a series/parallel array structure has been fabricated, in which the cell voltage and output power can easily be adjusted as required by printing. The output of the fabricated 4‐series/4‐parallel biofuel cell reached 0.97±0.02 mW at 1.4 V, which is the highest output power reported to date for a paper‐based biofuel cell. This work contributes to the development of flexible, wearable energy storage device.

We demonstrate, for the first time, the multiplexed determination of microbial species from whole blood using the paper‐folding technique of origami to enable the sequential steps of DNA extraction, loop‐mediated isothermal amplification (LAMP), and array‐based fluorescence detection. A low‐cost handheld flashlight reveals the presence of the final DNA amplicon to the naked eye, providing a “sample‐to‐answer” diagnosis from a finger‐prick volume of human blood, within 45 min, with minimal user intervention. To demonstrate the method, we showed the identification of three species of Plasmodium, analyzing 80 patient samples benchmarked against the gold‐standard polymerase chain reaction (PCR) assay in an operator‐blinded study. We also show that the test retains its diagnostic accuracy when using stored or fixed reference samples.

Advanced carbon materials are important for the next-generation of energy storage apparatus, such as electrochemical capacitors. Here, the physical and electrochemical properties of carbonised filter paper (FP) were investigated. FP is comprised of pure cellulose and is a standardised material. After carbonisation at temperatures ranging from 600 to 1700 °C, FP was contaminant-free, containing only carbon and some oxygenated species, and its primary fibre structure was retained (diameter ≈20–40 μm). The observed enhancement in conductivity of the carbonised FP was correlated with the carbonisation temperature. Electrochemical capacitance in the range of ≈1.8–117 F g−1 was achieved, with FP carbonised at 1500 °C showing the best performance. This high capacitance was stable with >87 % retained after 3000 charge–discharge cycles. These results show that carbonised FP, without the addition of composite materials, exhibits good supercapacitance performance, which competes well with existing electrodes made of carbon-based materials. Furthermore, given the lower cost and renewable source, cellulose-based materials are the more eco-friendly option for energy storage applications.

Carbonaceous materials, especially with graphite‐layers structure, as anode for potassium‐ion batteries (PIBs), are the footstone for industrialization of PIBs. However, carbonaceous materials with graphite‐layers structure usually suffer from poor cycle life and inferior stability, not to mention freestanding and flexible PIBs. Here, a freestanding and flexible 3D hybrid architecture by introducing carbon dots on the reduced graphene oxide surface (CDs@rGO) is synthesized as high performance PIBs anode. The CDs@rGO paper has efficient electron and ion transfer channels due to its unique structure, thus enhancing reaction kinetics. In addition, the CDs provide abundant defects and oxygen‐containing functional groups, which can improve the electrochemical performance. This freestanding and flexible anode exhibits the high capacity of 310 mAh g−1 at 100 mA g−1, ultra‐long cycle life (840 cycles with a capacity of 244 mAh g−1 at 200 mA g−1), and excellent rate performance (undergo six consecutive currents changing from 100 to 500 mA g−1, high capacity 185 mAh g−1 at 500 mA g−1), outperforming many existing carbonaceous PIB anodes. The results may provide a starting point for high‐performance freestanding and flexible PIBs and promote the rapid development of next‐generation flexible batteries., A freestanding and flexible 3D hybrid architecture by introducing carbon dots on the reduced graphene oxide surface is synthesized as a high‐performance potassium‐ion battery anode. It may provide a starting point for high‐performance freestanding and flexible potassium‐ion battery and promote the rapid development of next‐generation flexible batteries.

A novel ultra‐low‐cost biochemical analysis platform to quantify protein dissociation binding constants and kinetics using paper microfluidics is reported. This approach marries video imaging with one of humankind's oldest materials: paper, requiring no large, expensive laboratory equipment, complex microfluidics or external power. Temporal measurements of nanoparticle–antibody conjugates binding on paper is found to follow the Langmuir Adsorption Model. This is exploited to measure a series of antibody–antigen dissociation constants on paper, showing excellent agreement with a gold‐standard benchtop interferometer. The concept is demonstrated with a camera and low‐end smartphone, 500‐fold cheaper than the reference method, and can be multiplexed to measure ten reactions in parallel. These findings will help to widen access to quantitative analytical biochemistry, for diverse applications spanning disease diagnostics, drug discovery, and environmental analysis in resource‐limited settings.

Soft actuators have demonstrated potential in a range of applications, including soft robotics, artificial muscles, and biomimetic devices. However, the majority of current soft actuators suffer from the lack of real‐time sensory feedback, prohibiting their effective sensing and multitask function. Here, a promising strategy is reported to design bilayer electrothermal actuators capable of simultaneous actuation and sensation (i.e., self‐sensing actuators), merely through two input electric terminals. Decoupled electrothermal stimulation and strain sensation is achieved by the optimal combination of graphite microparticles and carbon nanotubes (CNTs) in the form of hybrid films. By finely tuning the charge transport properties of hybrid films, the signal‐to‐noise ratio (SNR) of self‐sensing actuators is remarkably enhanced to over 66. As a result, self‐sensing actuators can actively track their displacement and distinguish the touch of soft and hard objects.

A MnI‐catalyzed hydroboration of terminal alkenes and a 1,2‐diboration of terminal alkynes with pinacolborane (HBPin) is described. For alkenes, anti‐Markovnikov hydroboration takes place; for alkynes the reaction proceeds with excellent trans‐1,2‐selectivity. The most active pre‐catalyst is bench‐stable alkyl bisphosphine MnI complex fac‐[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn–alkyl bond to yield an acyl intermediate, which undergoes B−H bond cleavage of HBPin (for alkenes) and rapid C−H bond cleavage (for alkynes), forming the active MnI boryl and acetylide catalysts [Mn(dippe)(CO)2(BPin)] and [Mn(dippe)(CO)2(C≡CR)], respectively. A broad variety of aromatic and aliphatic alkenes and alkynes was efficiently and selectively borylated. Mechanistic insights are provided based on experimental data and DFT calculations revealing that an acceptorless reaction is operating involving dihydrogen release., A MnI‐catalyzed hydroboration of terminal alkenes and the 1,2‐diboration of terminal alkynes with pinacolborane is described. In the case of alkenes anti‐Markovnikov hydroboration takes place, while in the case of alkynes the reaction proceeds with trans‐1,2‐selectivity.

Herein we report unprecedented location‐dependent, size‐selective binding to designed lanthanide (Ln3+) sites within miniature protein coiled coil scaffolds. Not only do these engineered sites display unusual Ln3+ selectivity for moderately large Ln3+ ions (Nd to Tb), for the first time we demonstrate that selectivity can be location‐dependent and can be programmed into the sequence. A 1 nm linear translation of the binding site towards the N‐terminus can convert a selective site into a highly promiscuous one. An X‐ray crystal structure, the first of a lanthanide binding site within a coiled coil to be reported, coupled with CD studies, reveal the existence of an optimal radius that likely stems from the structural constraints of the coiled coil scaffold. To the best of our knowledge this is the first report of location‐dependent metal selectivity within a coiled coil scaffold, as well as the first report of location‐dependent Ln3+ selectivity within a protein., Location‐dependent size selectivity can be programmed into designed metallo coiled coils, allowing for the generation of near‐identical selective and promiscuous metal‐ion sites. The first crystal structure of a lanthanide bound within a coiled coil reveals that the existence of an optimal radius stems from the structural constraints of the peptide scaffold. Therefore, a selective site can in principle be designed de novo for any given Ln3+ ion.

Reduction of [SmIII(COT1,4‐SiiPr3)(BH4)(thf)] (COT1,4‐SiiPr3=1,4‐( i Pr3Si)3C8H6) with KC8 resulted in [SmIII/II/III(COT1,4‐SiiPr3)4], the first example of a homoleptic lanthanide quadruple‐decker. As indicated by an analysis of the bond metrics in the solid‐state, the inner Sm ion is present in the divalent oxidation state, while the outer ones are trivalent. This observation could be confirmed by quantum chemical calculations. Mechanistic studies revealed not only insight into possible formation pathways of [SmIII/II/III(COT1,4‐SiiPr3)4] but also resulted in the transformation to other mixed metal sandwich complexes with unique structural properties. These are the 1D‐polymeric chain structured [KSmIII(COT1,4‐SiiPr3)] n and the hexametallic species [(tol)K(COT1,4‐SiiPr3)SmII(COT1,4‐SiiPr3)K]2 which were initially envisioned as possible building blocks as part of different retrosynthetically guided pathways that we developed., The synthesis of the first well‐defined neutral and homoleptic (same metal, same ligand) all‐carbon‐based quadruple‐decker complexes [SmIII/II/III 3(COT1,4‐SiiPr3)4] (COT1,4‐SiiPr3=1,4‐( i Pr3Si)3C8H6) along with other unique sandwich complexes is shown.

The prezizane‐type sesquiterpene agarozizanol B was synthesized employing a photochemical cascade reaction as the key step. Starting from a readily available 1‐indanone with a tethered olefin, a strained tetracyclic skeleton was assembled which contained all carbon atoms of the sesquiterpene with the correct relative configuration. The conversion into the tricyclic prezizane skeleton was accomplished by a strategic cyclopropane bond cleavage. Prior to the cyclopropane ring opening an adaption of the oxidation state was required, which could be combined with a reductive resolution step. After removal of two functional groups, the natural product was obtained both in racemic form or, if resolved, as the (+)‐enantiomer which was shown to be identical to the natural product., Starting from a simple indanone derivative, diastereomerically pure intermediate 1 was formed in a photochemical cascade and served as precursor to agarozizanol B (2), either as racemate or as single enantiomer after a resolution step.

A series of novel heteroditopic halogen bonding (XB) receptor functionalised silica based materials, containing mono‐ and bis‐iodotriazole benzo‐15‐crown‐5 groups are investigated for the cooperative binding and extraction of sodium halide ion‐pair species from aqueous solution. Characterisation of the XB materials by CHN elemental analysis, 13C CP/MAS NMR and ATR‐FTIR spectroscopies confirms and quantifies the successful incorporation of the ion‐pair receptor frameworks to the silica material. ICP‐MS solid‐liquid extraction studies demonstrate the bidentate XB functionalised material is capable of NaI extraction from water. Importantly, cooperative XB‐mediated sodium halide ion‐pair binding is determined to be crucial to the material's extraction capabilities, impressively demonstrating a two‐fold enhancement in sodium iodide extraction efficiency relative to a heteroditopic hydrogen bonding receptor functionalised silica material analogue., A series of halogen bonding (XB) heteroditopic ion‐pair receptors comprising of benzo15‐crown‐5 cation binding moieties and iodotriazole XB donors are covalently integrated into silica QuadraSilTM based solid supports. Investigations into their sodium halide extraction capabilities demonstrated their ability as NaI extraction agents from water. Comparison with HB analogues demonstrate the crucial role of XB‐mediated NaI ion‐pair binding in the extraction performance.

We have synthesized the first isolable geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6‐trimethylphenyl (2 a,b), L=THF for (2 a) or [18]‐crown‐6 for (2 b)), a new synthon for the synthesis of organometallic reagents. The formation of these derivatives was confirmed by NMR spectroscopy and X‐ray crystallographic analysis. The UV/Vis spectra of these anions show three distinct bands, which were assigned by DFT calculations. The efficiency of 2 a,b to serve as new building block in macromolecular chemistry is demonstrated by the reactions with two different types of electrophiles (acid chlorides and alkyl halides). In all cases the salt metathesis reaction gave rise to novel Ge‐based photoinitiators in good yields., A convenient method to obtain geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6‐trimethylphenyl (1 a,b), L=THF for (1 a) or [18]‐crown‐6 for (1 b)), a new synthon for the synthesis of organometallic reagents, is reported. Selected examples of electrophiles were used to display the efficiency of 1 a,b as new building blocks in organometallic chemistry.

Garsubellin A is a meroterpene capable of enhancing the enzyme choline acetyltransferase whose decreased level is believed to play a central role in the symptoms of Alzheimer's disease. Due to the potentially useful biological activity together with the novel bridged and fused cyclic molecular architecture, garsubellin A has garnered substantial synthetic interest, but its absolute stereostructure has been undetermined. We report here the first enantioselective total synthesis of (+)‐garsubellin A. Our synthesis relies on stereoselective fashioning of a cyclohexanone framework and double conjugate addition of 1,2‐ethanedithiol that promotes aldol cyclization to build the bicyclic [3.3.1] skeleton. The twelve‐step, protecting group‐free synthetic route has enabled the syntheses of both the natural (−)‐garsubellin A and its unnatural (+)‐antipode for biological evaluations., The first enantioselective total synthesis of garsubellin A establishes the absolute stereostructure of the plant‐derived meroterpene that enhances the choline acetyltransferase enzyme responsible for the biosynthesis of the neurotransmitter acetylcholine. The 12‐step, protecting group‐free synthesis features use of a dithiolane for efficient construction of the bridged and fused ring system.

Recent improvements in mRNA display have enabled the selection of peptides that incorporate non‐natural amino acids, thus expanding the chemical diversity of macrocycles beyond what is accessible in nature. Such libraries have incorporated non‐natural amino acids at the expense of natural amino acids by reassigning their codons. Here we report an alternative approach to expanded amino‐acid diversity that preserves all 19 natural amino acids (no methionine) and adds 6 non‐natural amino acids, resulting in the highest sequence complexity reported to date. We have applied mRNA display to this 25‐letter library to select functional macrocycles that bind human STING, a protein involved in immunoregulation. The resulting STING‐binding peptides include a 9‐mer macrocycle with a dissociation constant (K D) of 3.4 nM, which blocks binding of cGAMP to STING and induces STING dimerization. This approach is generalizable to expanding the amino‐acid alphabet in a library beyond 25 building blocks., In vitro selection of macrocyclic peptides from a library that uses a 25‐amino‐acid alphabet has allowed the identification of peptides that block binding of human STING to its natural ligand and induce dimerization of STING monomers. Our method splits multiple degenerate codons and reassigns them to non‐natural amino acids.

A visible light‐switchable buffer system based on a merocyanine photoacid is presented. Para‐substitution of the indolium side with a methoxy group affords a compound suitable for making hydrolytically stable aqueous buffers whose pH can be tuned between 7 and 4 using 500 nm light., We show that protonated merocyanines can act as reversible photoacids even when buffered with NaOH, attaining tunable and fully reversible jumps of up to 3 pH units between pH 7 and 4.

There is an urgent need to develop antiviral drugs and alleviate the current COVID‐19 pandemic. Herein we report the design and construction of chimeric oligonucleotides comprising a 2′‐OMe‐modified antisense oligonucleotide and a 5′‐phosphorylated 2′‐5′ poly(A)4 (4A2‐5) to degrade envelope and spike RNAs of SARS‐CoV‐2. The oligonucleotide was used for searching and recognizing target viral RNA sequence, and the conjugated 4A2‐5 was used for guided RNase L activation to sequence‐specifically degrade viral RNAs. Since RNase L can potently cleave single‐stranded RNA during innate antiviral response, degradation efficiencies with these chimeras were twice as much as those with only antisense oligonucleotides for both SARS‐CoV‐2 RNA targets. In pseudovirus infection models, chimera‐S4 achieved potent and broad‐spectrum inhibition of SARS‐CoV‐2 and its N501Y and/or ΔH69/ΔV70 mutants, indicating a promising antiviral agent based on the nucleic acid‐hydrolysis targeting chimera (NATAC) strategy., Based on the strategy of nucleic acid hydrolysis targeting chimera, 5′‐phosphorylated 2′‐5′‐poly(A)4‐modified chimeric oligonucleotides were developed for enhanced degradation of the envelope or spike RNA of SARS‐CoV‐2 in vitro. The oligonucleotides can recognize specific viral RNA sequences and 2′‐5′ poly(A)4 can activate RNase L to cleave them specifically.

This communication reports experimental and theoretical evidences of σ‐hole interactions in adducts between nitrogen or oxygen nucleophiles and tetroxides of osmium or other group 8 elements. Cocrystals between pyridine or pyridine N‐oxide derivatives and osmium tetroxide are characterized through various techniques and rationalized as σ‐hole interactions using DFT calculations and several other computational tools. We propose the term “osme bond” (OmB, Om=Fe, Ru, Os, (Hs)) for naming the noncovalent interactions wherein group 8 elements have the role of the electrophile. The word osme is the transcription of ὀσμή, the ancient Greek word for smell that was used to name the heaviest group 8 element in relation to the smoky odor of its tetroxide., σ‐Hole interactions in adducts between nitrogen or oxygen nucleophiles and tetroxides of osmium or other group 8 elements are reported. Cocrystals between pyridine or pyridine N‐oxide derivatives and osmium tetroxide are characterized through various techniques including computational tools. We propose the term “osme bond” (OmB, Om=Fe, Ru, Os, (Hs)) for naming the noncovalent interactions wherein group 8 elements have the role of the electrophile.

A reinvestigation of the linalool synthase from Chryseobacterium polytrichastri uncovered its diterpene synthase activity, yielding polytrichastrene A and polytrichastrol A with new skeletons, besides known wanju‐2,5‐diene and thunbergol. The enzyme mechanism was investigated by isotopic labeling experiments and DFT calculations to explain an unusual ethyl group formation. Rationally designed exchanges of active site residues showed major functional switches, resulting for I66F in the production of five more new compounds, including polytrichastrene B and polytrichastrol B, while A87T, A192V and the double exchange A87T, A192V gave a product shift towards wanju‐2,5‐diene., Linalool synthase from Chryseobacterium polytrichastri was found to have diterpene synthase activity and produced diterpenes with new skeletons containing a rare ethyl group. Its formation was mechanistically studied through isotopic labeling and DFT calculations. Exchange of active site residues resulted in a functional switch leading to additional novel diterpenes. This work lays the ground for future rational engineering of terpene synthases.

The first chemical total synthesis of the highly oxygenated polyketide enterocin has been accomplished. The key step of the synthesis was a late‐stage biomimetic reaction cascade involving two intramolecular aldol reactions in which each step proceeded in 52 % yield (averaged) and which established four of the seven stereogenic centers. The pivotal precursor for the cascade reaction was assembled from three readily available building blocks. A chiral dithioacetal with two stereogenic centers originating from L‐arabinose represented the core fragment to both ends of which the other building blocks were attached by aldol reactions. The remaining stereogenic center was installed by Davis oxygenation immediately prior to the key step., Entering Nature's Design Office: The highly oxygenated natural product enterocin, which has so far resisted total synthetic attempts, was obtained in a biomimetic key step from triketone 1, which in turn was assembled from an L‐arabinose‐derived core fragment with a defined absolute configuration.

[EN] HPM-16 is a highly porous germanosilicate zeolite with an interrupted framework that contains a three-dimensional system of 12+10 10(12) 12+10-membered ring (MR) pores. The 10(12) MR pore in the b direction is a 10 MR pore with long 12 MR stretches forming 30 long tubular supercages. Along one direction the 10 MR pores are fused, meaning that the separation between adjacent pores consists of a single tetrahedron that is, additionally, connected to only three additional tetrahedra (a Q3). These fused pores are thus decorated by T-OH groups along the whole diffusion path, creating a hydrophilic region embedded in an otherwise essentially hydrophobic environment. The structure is built from highly porous 12 12 12 MR uninterrupted layers that are connected to each other through Q3 producing a second system of 10 10 10 MRpores. This zeolite can be extensively degermanated yielding a material with high thermal stability, despite its interrupted nature., The authors are grateful for financial support to the Spanish Ministry of Science Innovation and Universities (MICIU) (PID2019-105479RB-I00 project, AEI, Spain and FEDER, EU). SRGB also thanks MICIU for a Juan de la Cierva- Formación Research Contract (FJC2018-035697-I code reference). Synchrotron experiments were performed at beamline BL04 (MSPD) at the Spanish ALBA Synchrotron with the collaboration of ALBA staff, and special thanks are due to A. Manj n and A. Missiul. Centro T cnico Inform tico-CSIC, Trueno cluster facility of SGAI-CSIC is acknowledged for running the calculations. We also deeply thank C. Márquez- Álvarez for his kind help in characterization. The cRED data were collected at the Electron Microscopy Center (EMC), Department of Materials and Environmental Chemistry (MMK) in Stockholm University with the support of Knut and Alice Wallenberg (KAW) foundation-financed project 3DEM-NATUR.

A big problem with the chemistry literature is that it is not standardized with respect to precise operational parameters, and real time corrections are hard to make without expert knowledge. This lack of context means difficult reproducibility because many steps are ambiguous, and hence depend on tacit knowledge. Here we present the integration of online NMR into an automated chemical synthesis machine (CSM aka. “Chemputer” which is capable of small‐molecule synthesis using a universal programming language) to allow automated analysis and adjustment of reactions on the fly. The system was validated and benchmarked by using Grignard reactions which were chosen due to their importance in synthesis. The system was monitored in real time using online‐NMR, and spectra were measured continuously during the reactions. This shows that the synthesis being done in the Chemputer can be dynamically controlled in response to feedback optimizing the reaction conditions according to the user requirements., A universal chemical synthesis platform was extended by online NMR to allow adjustments of the encoded reactions on the fly. The approach was demonstrated on the class of Grignard reactions showing robust analytical results under harsh conditions. Real‐time process analytics and the use of straightforward feedback control algorithm enhance the usability of available synthesis formula considering existing deviations.

Herein, we disclose a recyclable, hybrid manganese catalyst for site‐selective azine C−H activation by weak amide assistance. The novel, reusable catalyst enabled C3–H arylation and C3–H alkylation with ample scope, and was characterized by detailed transmission electron microscopy analysis., A recyclable hybrid‐manganese catalyst was developed for site‐selective azine C−H activation by weak amide‐assistance with ample substrate scope. The heterogeneous catalyst proved to be reusable, and was analyzed in detail by spectroscopy, spectrometry and transmission electron microscopy.

Cyclophane structures can control steric pressure in the otherwise open spaces of square‐planar d8‐metal catalysts. This elegant concept was so far limited to symmetrical coordinated metals. We report how a cyclophane motif can be generated in ligands that chelate via two different donors. An ancillary second imine in the versatile κ2‐N,O‐salicylaldiminato catalyst type enables ring closure via olefin metathesis and selective double bond hydrogenation to yield a 30‐membered ring efficiently. Experimental and theoretical analyses show the ancillary imine is directed away from the active site and inert for catalysis. In ethylene polymerization the cyclophane catalyst is more active and temperature stable vs. an open structure reference, notably also in polar solvents. Increased molecular weights and decreased degrees of branching can be traced to an increased energy of sterically demanding transition states by the encircling cyclophane while chain propagation remains highly efficient., We demonstrate how a cyclophane structure can be generated in square‐planar complexes with two different chelating donors (N,O). An ancillary second imine function in the versatile κ 2‐N,O‐salicylaldiminato catalyst type enables ring closure between two symmetrical 4′,4′′‐diallyl substituted terphenyl motifs.

Radical polymerization with reversible addition‐fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well‐defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side‐reactions and high spatio‐temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low‐energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C−S bond is induced upon low‐energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group (.CH3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment., Electron attachment leads to the efficient dissociation of carbonothioylsulfanyl molecules which are relevant for Reversible Addition‐Fragmentation chain Transfer (RAFT) polymerization. We show that the preferred C−S bond cleavage can be initiated by an electron with almost no kinetic energy, in contrast to other dissociation reactions. This feature leads to a pronounced control of bond dissociation upon electron attachment.

Atropo‐enantioselective biaryl coupling through C−H bond functionalization is an emerging technology allowing direct construction of axially chiral molecules. This approach is largely limited to electrophilic coupling partners. We report a highly atropo‐enantioselective C−H arylation of tetralone derivatives paired with aryl boronic esters as nucleophilic components. The transformation is catalyzed by chiral cyclopentadienyl (Cpx) iridium(III) complexes and enabled by oxidatively enhanced reductive elimination from high‐valent cyclometalated Ir‐species., A highly atropo‐enantioselective C−H arylation of tetralone derivatives paired with aryl boronic esters as nucleophilic components is presented. The transformation is catalyzed by chiral cyclopentadienyl (Cpx) iridium(III) complexes and enabled by oxidatively enhanced reductive elimination from high‐valent cyclometalated Ir‐species.

Dysregulation of post‐translational modifications (PTMs) like phosphorylation is often involved in disease. NMR may elucidate exact loci and time courses of PTMs at atomic resolution and near‐physiological conditions but requires signal assignment to individual atoms. Conventional NMR methods for this base on tedious global signal assignment that may often fail, as for large intrinsically disordered proteins (IDPs). We present a sensitive, robust alternative to rapidly obtain only the local assignment near affected signals, based on FOcused SpectroscopY (FOSY) experiments using selective polarisation transfer (SPT). We prove its efficiency by identifying two phosphorylation sites of glycogen synthase kinase 3 beta (GSK3β) in human Tau40, an IDP of 441 residues, where the extreme spectral dispersion in FOSY revealed unprimed phosphorylation also of Ser409. FOSY may broadly benefit NMR studies of PTMs and other hotspots in IDPs, including sites involved in molecular interactions., A new suite of 2D FOSY experiments focuses on one coupled nuclear spin system at a time, that is, a PTM site or a structural hotspot in general, with 3–5 known frequencies. With higher sensitivity and versatility than achievable by traditional experiments, FOSY solves the spectral dispersion problem and obtains only the relevant local NMR signal assignment in a few hours, as demonstrated for two phosphorylation sites in the 441‐residue IDP Tau.

Post‐synthetic modification (PSM) of the interpenetrated diamondoid metal–organic framework (Me2NH2)[In(BDC‐NH2)2] (BDC‐NH2=aminobenzenedicarboxylate) SHF‐61 proceeds quantitatively in a single‐crystal‐to‐single‐crystal manner to yield the acetamide derivative (Me2NH2)[In(BDC‐NHC(O)Me)2] SHF‐62. Continuous breathing behaviour during activation/desolvation is retained upon PSM, but pore closing now leads to ring‐flipping to avert steric clash of amide methyl groups of the modified ligands. This triggers a reduction in the amplitude of the breathing deformation in the two dimensions associated with pore diameter, but a large increase in the third dimension associated with pore length. The MOF is thereby converted from predominantly 2D breathing (in SHF‐61) to a distinctly 3D breathing motion (in SHF‐62) indicating a decoupling of the pore‐width and pore‐length breathing motions. These breathing motions have been mapped by a series of single‐crystal diffraction studies., Post‐synthetic modification of diamondoid MOF SHF‐61 generates its methylamide analogue [(Me2NH2)[In(BDC‐NH(CO)Me)], SHF‐62, as single crystals. Resulting ligand steric demands and H‐bonding capability lead to a change in dimensionality of the MOF breathing behaviour from 2D breathing (pore width) to 3D breathing (pore width and length), which has been mapped by single‐crystal X‐ray diffraction.

We report the functionalization of cysteine residues with lipophilic alkynes bearing a silyl group or an alkyl chain using amphiphilic ethynylbenziodoxolone reagents (EBXs). The reactions were carried out in buffer (pH 6 to 9), without organic co‐solvent or removal of oxygen, either at 37 °C or room temperature. The transformation led to a significant increase of peptide lipophilicity and worked for aromatic thiols, homocysteine, cysteine, and peptides containing 4 to 18 amino acids. His6‐Cys‐Ubiquitin was also alkynylated under physiological conditions. Under acidic conditions, the thioalkynes were converted into thioesters, which could be cleaved in the presence of hydroxylamine., Amphiphilic hypervalent iodine reagents enable the alkynylation of cysteine residues in peptides with lipophilic groups in water. The reaction proceeds in neutral standard buffers with high efficiency for a broad range of peptides and one protein. The thioalkynes can be converted into cleavable thioesters under acidic conditions.

DNA polymerase β (Pol β) is a frequently overexpressed and/or mutated bifunctional repair enzyme. Pol β possesses polymerase and lyase active sites, that are employed in two steps of base excision repair. Pol β is an attractive therapeutic target for which there is a need for inhibitors. Two mechanistically inspired covalent inhibitors (1, IC50=21.0 μM; 9, IC50=18.7 μM) that modify lysine residues in different Pol β active sites are characterized. Despite modifying lysine residues in different active sites, 1 and 9 inactivate the polymerase and lyase activities of Pol β. Fluorescence anisotropy experiments indicate that they do so by preventing DNA binding. Inhibitors 1 and 9 provide the basis for a general approach to preparing domain selective inhibitors of bifunctional polymerases. Such molecules could prove to be useful tools for studying the role of wild type and mutant forms of Pol β and other polymerases in DNA repair., A single synthesis and screening strategy yields covalent inhibitors that inactivate bifunctional DNA polymerase β by modifying lysine residues in different active site domains and prevent DNA binding.

Trifluoromethoxylated (hetero)arenes are of great interest for several disciplines, especially in agro‐ and medicinal chemistry. Radical C−H trifluoromethoxylation of (hetero)arenes represents an attractive approach to prepare such compounds, but the high cost and low atom economy of existing .OCF3 radical sources make them unsuitable for the large‐scale synthesis of trifluoromethoxylated building blocks. Herein, we introduce bis(trifluoromethyl)peroxide (BTMP, CF3OOCF3) as a practical and efficient trifluoromethoxylating reagent that is easily accessible from inexpensive bulk chemicals. Using either visible light photoredox or TEMPO catalysis, trifluoromethoxylated arenes could be prepared in good yields under mild conditions directly from unactivated aromatics. Moreover, TEMPO catalysis allowed for the one‐step synthesis of valuable pyridine derivatives, which have been previously prepared via multi‐step approaches., Bis(trifluoromethyl)peroxide (BTMP) is introduced as a new reagent for the C−H trifluoromethoxylation of arenes and heteroarenes. Readily accessed from inexpensive bulk chemicals, BTMP serves as a practical source of •OCF3 radicals upon activation through either visible light photoredox or TEMPO catalysis. Both methods deliver valuable fluorine‐containing building blocks in a single step from (hetero)aromatic feedstocks.

Linear or branched 1,3‐diketone‐linked thymidine 5′‐O‐mono‐ and triphosphate were synthesized through CuAAC click reaction of diketone‐alkynes with 5‐azidomethyl‐dUMP or ‐dUTP. The triphosphates were good substrates for KOD XL DNA polymerase in primer extension synthesis of modified DNA. The nucleotide bearing linear 3,5‐dioxohexyl group (HDO) efficiently reacted with arginine‐containing peptides to form stable pyrimidine‐linked conjugates, whereas the branched 2‐acetyl‐3‐oxo‐butyl (PDO) group was not reactive. Reaction with Lys or a terminal amino group formed enamine adducts that were prone to hydrolysis. This reactive HDO modification in DNA was used for bioconjugations and cross‐linking with Arg‐containing peptides or proteins (e.g. histones)., Arginine‐specific 1,3‐diketone‐linked reactive nucleotides are reported for the enzymatic construction of DNA probes and cross‐linking with peptides and proteins.

Modafinil, a widely used psychoactive drug, has been shown to exert a positive impact on cognition and is used to treat sleep disorders and hyperactivity. Using time‐of‐flight secondary ion mass spectrometric imaging, we studied the changes of brain lipids of Drosophila melanogaster induced by modafinil to gain insight into the functional mechanism of modafinil in the brain. We found that upon modafinil treatment, the abundance of phosphatidylcholine and sphingomyelin species in the central brain of Drosophila is significantly decreased, whereas the levels of phosphatidylethanolamine and phosphatidylinositol in the brains show significant enhancement compared to the control flies. The alteration of brain lipids caused by modafinil is consistent with previous studies about cognition‐related drugs and offers a plausible mechanism regarding the action of modafinil in the brain as well as a potential target for the treatment of certain disorders., Modafinil, used for sleep disorder treatment, appears to enhance attention as well as improve learning and memory. Imaging mass spectrometry is used to investigate the effects of modafinil on the alteration of lipid composition on fly brain. Modafinil induces a decrease in PC and SM contents and increases the levels of PEs and PIs. The lipid changes caused by modafinil are similar to the effects of methylphenidate, which also improves cognition.

We present a mechanistic study on the formation and dynamic changes of a ligand‐based heterogeneous Pd catalyst for chemoselective hydrogenation of α,β‐unsaturated aldehyde acrolein. Deposition of allyl cyanide as a precursor of a ligand layer renders Pd highly active and close to 100 % selective toward propenol formation by promoting acrolein adsorption in a desired configuration via the C=O end. Employing a combination of real‐space microscopic and in‐operando spectroscopic surface‐sensitive techniques, we show that an ordered active ligand layer is formed under operational conditions, consisting of stable N‐butylimine species. In a competing process, unstable amine species evolve on the surface, which desorb in the course of the reaction. Obtained atomistic‐level insights into the formation and dynamic evolution of the active ligand layer under operational conditions provide important input required for controlling chemoselectivity by purposeful surface functionalization., We present a mechanistic study on the formation and dynamic changes of a ligand‐based heterogeneous Pd catalyst for chemoselective hydrogenation of α,β‐unsaturated aldehyde acrolein. Deposition of allyl cyanide as a precursor of a ligand layer renders Pd highly active and close to 100 % selective toward propenol formation by promoting acrolein adsorption in a desired configuration via the C=O end.

The development of chemosensors to detect analytes in biologically relevant solutions is a challenging task. We report the synthesis of a fluorescent receptor that combines vibration‐induced emission (VIE) and dynamic covalent chemistry for the detection of glucose in aqueous media. We show that the bis‐2‐(N‐methylaminomethyl)phenylboronic acid‐decorated N,N′‐diphenyl‐dihydrodibenzo[a,c]phenazine (DPAC) receptor 1 can detect glucose and discriminate between closely related monosaccharides including those commonly found in blood. Preliminary studies suggest monosaccharides bind to the DPAC‐receptor with a 1:1 stoichiometry to produce pseudomacrocyclic complexes, which in turn leads to distinct optical changes in the fluorescent emission of the receptor for each host. Moreover, the complexation‐induced change in emission can be detected visually and quantified in a ratiometric way. Our results highlight the potential of VIE‐type receptors for the quantitative determination of saccharides in biological samples., A novel sugar fluorescent chemosensor which combines a vibrational‐induced‐emission (VIE)‐active DPAC core and two N‐methylaminomethylphenylboronic acid moieties can detect glucose within seconds and discriminate between closely related monosaccharides including those commonly found in blood.

The first examples of monolithic crystalline host–guest hybrid materials are described. The reaction of 1,3,5‐benzenetricarboxylic acid (H3BTC) and Fe(NO3)3⋅9 H2O in the presence of decamethylcucurbit[5]uril ammonium chloride (MC5⋅2 NH4Cl⋅4 H2O) directly affords MC5@MIL‐100(Fe) hybrid monoliths featuring hierarchical micro‐, meso‐ and macropores. Particularly, this “bottle‐around‐ship” synthesis and one‐pot shaping are facilitated by a newly discovered Fe‐MC5 flowing gel formed by mechanochemistry. The designed MC5@MIL‐100(Fe) hybrid material with MC5 as active domains shows enhanced CH4 and lead(II) uptake performance, and selective capture of lead(II) cations at low concentrations. This shows that host–guest hybrid materials can exhibit synergic properties that out‐perform materials based on individual components., Mechanochemistry has been applied to achieve one‐pot fabrication of monolithic decamethylcucurbit[5]uril (MC5)‐encapsulating metal–organic frameworks. The designed MC5@MIL‐100(Fe) hybrid material with MC5 as active domains shows enhanced uptake, and selective capture of lead(II) cations at low concentrations. This work opens up the novel possibility of designing task‐specific porous host–guest hybrid materials on a macroscopic scale.

The syntheses, properties and application of the air‐stable electron acceptors, diindenopyrazines 4 a–g are reported demonstrating the introduction of functional aryl groups in the 6‐ and 12‐positions. The targets are accessible on the hundred milligram to gram scale. The structure of the aryl groups in 4 a–g modulates their solubility, redox potentials and optical properties. The introduction of electron‐poor aryl groups to the electron‐poor diindenopyrazine backbone reduces the electron affinity to −4 eV, making the compounds attractive as n‐semiconductors. A simple organic field‐effect transistor of 4 e –without optimization– shows electron transport with a mobility of up to 0.037 cm2 V−1 s−1., Electron poor, but rich in possibility: Electron‐deficient diindenopyrazines with different aryl substituents have been synthesized and characterized. The introduction of electron‐poor aryl groups reduces the electron affinity to −4 eV, thereby making the compounds attractive as n‐semiconductors. Tested in an organic field‐effect transistor, compound 4 e showed electron mobilities up to 0.037 cm2 V−1 s−1.

Diethynyl phosphinates were developed as bisfunctional electrophiles for the site‐selective modification of peptides, proteins and antibodies. One of their electron‐deficient triple bonds reacts selectively with a thiol and positions an electrophilic moiety for a subsequent intra‐ or intermolecular reaction with another thiol. The obtained conjugates were found to be stable in human plasma and in the presence of small thiols. We further demonstrate that this method is suitable for the generation of functional protein conjugates for intracellular delivery. Finally, this reagent class was used to generate functional homogeneously rebridged antibodies that remain specific for their target. Their modular synthesis, thiol selectivity and conjugate stability make diethynyl phosphinates ideal candidates for protein conjugation for biological and pharmaceutical applications., Diethynyl phosphonites were found to react specifically with two thiols in aqueous buffer to give constructs that are stable under physiological conditions. This enables the facile generation of protein (double)‐conjugates. Moreover, these molecules can be used to rebridge the interchain disulfides of therapeutic IgG antibodies.

A long‐term goal in realizing a sustainable biocatalysis and organic synthesis is the direct use of the greenhouse gas CO2 as feedstock for the production of bulk and fine chemicals, such as pharmaceuticals, fragrances and food additives. Here we developed a modular in vitro platform for the continuous conversion of CO2 into complex multi‐carbon compounds, such as monoterpenes (C10), sesquiterpenes (C15) and polyketides. Combining natural and synthetic metabolic pathway modules, we established a route from CO2 into the key intermediates acetyl‐ and malonyl‐CoA, which can be subsequently diversified through the action of different terpene and polyketide synthases. Our proof‐of‐principle study demonstrates the simultaneous operation of different metabolic modules comprising of up to 29 enzymes in one pot, which paves the way for developing and optimizing synthesis routes for the generation of complex CO2‐based chemicals in the future., Coupling of a synthetic CO2‐fixing cycle and a natural glyoxylate assimilation cycle with different biosynthetic pathways enables the sustainable production of terpenes and polyketides. Demonstration of this modular, multi‐enzyme in vitro platform sets the stage for a diversified synthesis of pharmaceuticals and commodity chemicals directly from CO2.

A series of highly substituted 1,2‐azaborinines, including a phenylene‐bridged bis‐1,2‐azaborinine, was synthesized from the reaction of 1,2‐azaborete rhodium complexes with variously substituted alkynes. 1‐Rhoda‐3,2‐azaborole complexes, which are accessible by phosphine addition to the corresponding 1,2‐azaborete complexes, were also found to be suitable precursors for the synthesis of 1,2‐azaborinines and readily reacted with alkynyl‐substituted 1,2‐azaborinines to generate new regioisomers of bi‐1,2‐azaborinines, which feature directly connected aromatic rings. Their molecular structures, which can be viewed as boron‐nitrogen isosteres of biphenyls, show nearly perpendicular 1,2‐azaborinine rings. The new method using rhodacycles instead of 1,2‐azaborete complexes as precursors is shown to be more effective, allowing the synthesis of a wider range of 1,2‐azaborinines., Boron‐nitrogen analogs of metallacyclopentadienes in the form of 1‐rhoda‐3,2‐azaboroles (see Figure) are shown to be suitable precursors for the synthesis of 1,2‐azaborinines. Comparisons with 1,2‐azaborete rhodium complexes demonstrate their superior reactivity towards alkynes, allowing to expand the range of 1,2‐azaborinines. A series of multiply substituted 1,2‐azaborinines, including a phenylene‐bridged derivative and rare bicyclic derivatives composed of two 1,2‐azaborinine rings linked by a single bond, are reported.

A 12‐step total synthesis of the natural product dysiherbol A, a strongly anti‐inflammatory and anti‐tumor avarane meroterpene isolated from the marine sponge Dysidea sp., was elaborated. As key steps, the synthesis features an enantioselective Cu‐catalyzed 1,4‐addition/enolate‐trapping opening move, an Au‐catalyzed double cyclization to build up the tetracyclic core‐carbon skeleton, and a late installation of the C5‐bridgehead methyl group via proton‐induced cyclopropane opening associated with spontaneous cyclic ether formation. The obtained pentacyclic compound (corresponding to an anhydride of the originally suggested structure for dysiherbol A) showed identical spectroscopic data as the natural product, but an opposite molecular rotation. CD‐spectroscopic measurements finally confirmed that both the constitution and the absolute configuration of the originally proposed structure of (+)‐dysiherbol A need to be revised., In a key step of the first enantioselective total synthesis of the anti‐inflammatory marine meroterpene dysiherbol A, the tetra‐carbocyclic core skeleton is set‐up in a unique gold‐catalyzed double cyclization, and the ether bridge of the pentacyclic target structure is spontaneously formed under cyclopropane opening upon deprotection of a late intermediate.

To create innovative materials, efficient control and engineering of pore sizes and their characteristics, crystallinity and stability is required. Eight hybrid Tri4Di6 imine cages with a tunable degree of fluorination and one fully fluorinated Tri4Di6 imine cage are investigated. Although the fluorinated and the non‐fluorinated building blocks used herein differ vastly in reactivity, it was possible to gain control over the outcome of the self‐assembly process, by carefully controlling the feed ratio. This represents the first hybrid material based on fluorinated/hydrogenated porous organic cages (POCs). These cages with unlimited miscibility in the solid state were obtained as highly crystalline samples after recrystallization and even showed retention of the crystal lattice, forming alloys. All mixtures and the fully fluorinated Tri4Di6 imine cage were analyzed by MALDI‐MS, single‐crystal XRD, powder XRD and in regard to thermal stability (TGA)., A supramolecular alloy, freely composed of eight hybrid Tri4Di6 imine cages with a tunable degree of fluorination can be created with high crystallinity. Although the fluorinated and the non‐fluorinated building blocks used herein differ vastly in reactivity, gaining control over the outcome of the self‐assembly process was achieved by carefully controlling the feed ratio.

n‐peri‐Acenes (n‐PAs) have gained interest as model systems of zigzag‐edged graphene nanoribbons for potential applications in nanoelectronics and spintronics. However, the synthesis of n‐PAs larger than peri‐tetracene remains challenging because of their intrinsic open‐shell character and high reactivity. Presented here is the synthesis of a hitherto unknown n‐PA, that is, peri‐heptacene (7‐PA), in which the reactive zigzag edges are kinetically protected with eight 4‐tBu‐C6H4 groups. The formation of 7‐PA is validated by high‐resolution mass spectrometry and in situ FT‐Raman spectroscopy. 7‐PA displays a narrow optical energy gap of 1.01 eV and exhibits persistent stability (t 1/2≈25 min) under inert conditions. Moreover, electron‐spin resonance measurements and theoretical studies reveal that 7‐PA exhibits an open‐shell feature and a significant tetraradical character. This strategy could be considered a modular approach for the construction of next‐generation (3 N+1)‐PAs (where N≥3)., The synthesis of the hitherto unknown peri‐heptacene 7‐PA is demonstrated by a rational molecular design strategy in which the reactive zigzag edges are kinetically protected. The formation of 7‐PA is validated by high‐resolution mass spectrometry and in situ FT‐Raman spectroscopy. The open‐shell 7‐PA displays a narrow optical energy gap of 1.01 eV and exhibits a persistent stability (half‐life ≈25 min) under inert conditions.

Dearomatization is an effective method to transform readily available N‐heterocycles into partially saturated motifs. Manipulation of dihydro‐derivatives holds great potential and provides access to a variety of semi‐saturated N‐heterocyclic building blocks. However, current strategies are limited in scope and the use of sensitive reagents restricts the applicability in synthetic laboratories. Herein, we report the synthesis of a broad variety of N‐substituted 1,4‐ and 1,2‐dihydropyridines by very mild and selective reduction with amine borane for the first time., Metal‐free dearomatization of N‐heteroarenes is a well‐known and powerful method to yield partially saturated N‐heterocyclic building blocks. Yet, the use of sensitive reagents restricts the applicability in synthetic laboratories. Herein, we present a very mild and selective reduction of N‐heteroarenes by amine borane to synthesize a broad variety of N‐substituted 1,4‐ and 1,2‐dihydropyridines.

Hexameric hemoprotein (HTHP) is employed as a scaffold protein for the supramolecular assembly and activation of the apoptotic signalling enzyme caspase‐9, using short DNA elements as modular recruitment domains. Caspase‐9 assembly and activation on the HTHP platform due to enhanced proximity is followed by combinatorial inhibition at high scaffold concentrations. The DNA recruitment domains allow for reversible switching of the caspase‐9 assembly and activity state using short modulatory DNA strands. Tuning of the recruitment domain affinity allows for generating kinetically trapped active enzyme complexes, as well as for dynamic repositioning of caspases over scaffold populations and inhibition using monovalent sink platforms. The conceptual combination of a highly structured multivalent protein platform with modular DNA recruitment domains provides emergent biomimicry properties with advanced levels of control over protein assembly., A hexameric protein recruitment platform allows controlled assembly and activation of caspase‐9 enzymes using short DNA sequences as modular recruitment domains. Simple molecular tuning of the DNA recruitment domains enables reversible switching or kinetic inhibition of the proximity‐induced enzyme activation.

A facile synthesis and isolation of pristine silicon tetrakis(trifluoromethanesulfonate), Si(OTf)4, is reported, acting as the first neutral silicon‐based Lewis superacid suitable towards soft and hard Lewis bases. Its OTf groups have a dual function: they are excellent leaving groups and modulate the degree of reactivity towards soft and hard Lewis bases. Exposed to soft Lewis donors, Si(OTf)4 leads to [L2Si(OTf)4] complexes (L=isocyanide, thioether and carbonyl compounds) with retention of all Si−OTf bonds. In contrast, it can cleave C−X bonds (X=F, Cl) of hard organic Lewis bases with a high tendency to form SiX4 (X=F, Cl) after halide/triflate exchange. Most notable, Si(OTf)4 allows a gentle oxydefluorination of mono‐ and bis(trifluoromethyl)benzenes, resulting in the formation of the corresponding benzoylium species, which are stabilized by the weakly coordinating [Si(OTf)6] dianion., The title compound is the first neutral silane acting as a hard and soft Lewis superacid as exemplified by extensive scaling. Its distinct reactivity towards soft Lewis bases L leads to unprecedented [L2Si(OTf)4] complexes, while the reactions with halocarbons afford electrophilic cations, including a straight access to benzoylium cations from mono‐ and bis(trifluoromethyl)benzenes, stabilized by the [Si(OTf)6]2− weakly coordinating dianion.

Supramolecular coordination cages show a wide range of useful properties including, but not limited to, complex molecular machine‐like operations, confined space catalysis, and rich host–guest chemistries. Here we report the uptake and release of non‐covalently encapsulated, pharmaceutically‐active cargo from an octahedral Pd cage bearing polymer chains on each vertex. Six poly(ethylene glycol)‐decorated bipyridine ligands are used to assemble an octahedral PdII 6(TPT)4 cage. The supramolecular container encapsulates progesterone and ibuprofen within its hydrophobic nanocavity and is activated by shear force produced by ultrasonication in aqueous solution entailing complete cargo release upon rupture, as shown by NMR and GPC analyses., An octahedral PdII 6(TPT)4 cage with polymer chains on each vertex is activated by shear force from ultrasonication in aqueous solution. The metal–organic cage encapsulates progesterone or ibuprofen within its hydrophobic nanocavity and shows complete cargo release upon rupture.

The vibrational spectroscopy of lithium dichloride anions microhydrated with one to three water molecules, [LiCl2(H2O)1–3]−, is studied in the OH stretching region (3800–2800 cm−1) using isomer‐specific IR/IR double‐resonance population labelling experiments. The spectroscopic fingerprints of individual isomers can only be unambiguously assigned after anharmonic effects are considered, but then yield molecular level insight into the onset of salt dissolution in these gas phase model systems. Based on the extent of the observed frequency shifts ΔνOH of the hydrogen‐bonded OH stretching oscillators solvent‐shared ion pair motifs (3200 cm−1). The characteristic fingerprint of a water molecule trapped directly in‐between two ions of opposite charge provides an alternative route to evaluate the extent of ion pairing in aqueous electrolyte solutions., Spectroscopic identification of solvent‐shared ion pairs: Isomer‐specific vibrational spectra of microhydrated lithium dichloride anions in the gas phase allow to unambiguously distinguish between contact and solvent‐shared ion pair cores. Red‐shifted OH stretching bands are corelated to characteristic ion‐water and water‐water interactions based on a comparison to anharmonic IR spectra from electronic structure calculations.

The first all‐metallocene rechargeable battery consisting of poly‐cobaltocenium/‐ and poly‐ferrocene/reduced graphene oxide composites as anode and cathode was prepared. The intrinsically fast ET self‐exchange rate of metallocenes was successfully combined with an efficient ion‐percolation achieved by molecular self‐assembly. The resulting battery materials show ideal Nernstian behavior, is thickness scalable up to >1.2 C cm−2, and exhibit high coulombic efficiency at ultrafast rates (200 A g−1). Using aqueous LiClO4, the charge is carried exclusively by the anion. The ClO4 − intercalation is accompanied by a reciprocal height change of the active layers. Principally, volume changes in organic battery materials during charging/discharging are not desirable and represent a major safety issue. However, here, the individual height changes—due to ion breathing—are reciprocal and thus prohibiting any internal pressure build‐up in the closed‐cell, leading to excellent cycling stability., An all‐metallocene battery consisting of poly‐ferrocene and poly‐cobaltocene is shown. The extremely high power density is provided via molecular self‐assembly between polymers and reduced graphene oxide. The precise construction of anode and cathode results in a reciprocal height change during charging–discharging, due to anion (de)intercalation in the soft structure.

The first example of a neutral spin‐delocalized carbon‐nanoring radical was achieved by integration of the open‐shell phenalenyl unit into cycloparaphenylene (CPP). Spin distribution in this hydrocarbon is localized primarily on the phenalenyl segment and partially on the CPP segment as a consequence of steric and electronic effects. The resulting geometry is reminiscent of a diamond ring, with pseudo‐perpendicular arrangement of the radial and the planar π‐surface. The phenylene rings attached directly to the phenalenyl unit give rise to a steric effect that governs a highly selective dimerization pathway, yielding a giant double nanohoop. Its π‐framework made of 158 sp2‐carbon atoms was elucidated by single‐crystal X‐ray diffraction, which revealed a three‐segment CPP‐peropyrene‐CPP structure. This nanocarbon shows a fluorescence profile characteristic of peropyrene, regardless of which segment gets excited. These results in conjunction with DFT suggest that adjusting the size of the CPP segments in this double nanohoop could deliver donor–acceptor systems., A neutral open‐shell carbon nanoring was achieved by integration of the phenalenyl unit into the cycloparaphenylene framework. It is shown that the spin distribution and reactivity of this hydrocarbon in the shape of a diamond ring are a result of steric and electronic effects and that selective dimerization yields a double nanohoop with a radial‐planar‐radial arrangement of its three π‐conjugated segments comprising a total of 158 sp2‐carbon atoms.