Die Kombination von DNA-Origami mit synthetischen Polymeren führt zu einer neuen Klasse von Materialien mit interessanten Eigenschaften und Merkmalen. Dieses Verfahren ist genauer als herkömmliche Nanofabrikationsverfahren, wie die Positionierung einzelner Polymerstränge. In diesem Kurzaufsatz fassen wir die mögliche Herstellung von Nanostrukturen von Polymeren mit zwei- und dreidimensionalem DNA-Origami zusammen.

Tricarbocyanine dyes are widely recognized as highly fluorescent compounds of use in a diverse range of biomedical and technical applications. This Minireview discusses the impact of different meso-substituents and how they may be used in the design of functional probes.

Obwohl Coenzyme im biotischen Metabolismus eine Schlüsselrolle spielen, standen sie als Beteiligte am Protometabolismus nicht im Mittelpunkt des Interesses, noch wurde ihre mögliche präbiotische Erzeugung ausführlich diskutiert. Dieser Aufsatz bietet einen konzeptionellen Überblick über die Rolle von Coenzymen mit Blick auf bekannte Theorien des Protometabolismus und ihre Aufnahme in die RNA-Welthypothese.

Photoangeregte Anionen wirken stark reduzierend und können als Katalysatoren oder als Reaktanten eingesetzt werden. In Gegenwart von Basen verschiebt sich die Absorption durch Deprotonierung im Vergleich zur neutralen Spezies bathochrom. Daher ist häufig eine Anregung mit sichtbarem Licht möglich.

A Ni phthalocyanine (NiPc) decorated by four methoxyethoxy units with a strong intramolecular electric field is prepared and used as hole-transporting materials (HTMs) in perovskite solar cells (PSCs). The best PSCs with NiPc as dopant-free HTM show a record efficiency of 21.23 % (certified 21.03 %). The PSCs also exhibit the excellent stability.

An enzyme-activatable engineering strategy was developed to generate a new DNAzyme sensor technology. The catalytic sensing probe remained silent in normal cells but could be reactivated by a cancer-specific enzyme, thus enabling metal-ion signals to be identified as occurring in tumor cells as opposed to normal cells both in vitro and in vivo (see picture).

An efficient asymmetric hydroesterfication of diarylmethyl carbinols is developed with a Pd-WingPhos catalyst, resulting in a series of chiral 4-aryl-3,4-dihydrocoumarins in excellent enantioselectivities and good yields. The method features mild reaction conditions, a broad substrate scope, use of easily accessible starting materials, and low palladium loadings. A plausible stereochemical model is proposed with the Pd-WingPhos catalyst.

Fluorophore labels that transiently bind to and unbind from a protein target allow photobleaching in super-resolution optical fluctuation imaging (SOFI) to be circumvented. Using short fluorophore-labeled DNA oligonucleotides, we demonstrate high-contrast, low-background, and multi-color super-resolution imaging with SOFI.

A readily available catalytic system composed of iron(II) chloride and 1,10-phenanthroline is widely applicable for the ring-closing C−H amination of N-benzoyloxyurea. High yields are provided both for activated and completely non-activated C−H bonds.

Live cells can be efficiently conjugated with nanoparticles on their surface by two successive bioorthogonal click reactions. The 2-step method yields a highly specific cell surface conjugation of ligand-decorated nanoparticles, with very low non-specific background binding.

Locally ordered graphitized carbon (LOGC), interconnected with disordered carbon, is able to weaken the van der Waals interactions between adjacent graphene sheets and thus reduce the anion-intercalating voltage. Conversely, disordered carbon not only interconnects the dispersed nanographite but also partially buffers severe anion–anion repulsions and offers extra capacitive anion storage sites.

Macroscopically oriented, large polar crystalline films were fabricated at the air–water interface by photoisomerization of a cis-arylazopyrazole derivative dissolved in the aqueous phase. The trans-film formed on the solid substrate showed reversible photo-induced phase changes between the polar crystal and liquid phase, which lead to an on/off photo-switching of the second-harmonic-generation intensity.

Self-pillared ultramicroporous carbon nanoplates have been prepared via a one-pot multi-component sequential condensation, which exhibit a high selectivity and fast diffusion kinetics for CH₄/N₂ separation.

A large-area cocrystal film is designed and fabricated in a low-cost solution-processed method. Attributed to the enhanced charge-transfer absorption in the NIR region, the generation of long-lived free carriers, and the device configuration optimization, the cocrystal film-based photodetector exhibits a high responsivity to a wide spectra range, coupled with fast response times and large EQE.

Surface modification with Cd atom doping generates the Au₁₉Cd₂(SR)₁₆ nanocluster, which exhibits significantly boosted CO₂ reduction reaction (CO₂RR) performance, doubling that of the undoped Au₂₃. DFT calculations reveal that local surface Cd doping leads to a dynamic behavior of the sulfur active site on Au₁₉Cd₂ when interacting with CO, contributing to the energetically favorable formation of CO on the exposed sulfur active site that facilitates the overall CO₂RR.

An operationally simple and easily scalable protocol for deuterogenolysis of carbon oxygen bonds was developed, which leads to a practical approach to synthetically valuable benzyl-deuterated building blocks and deuterium medicines, including atomoxetine, tesmilifene, amiodarone, and ibuprofen. Combining the in situ electrocatalytic heavy water-splitting, this protocol enables the direct utilization of D₂O for construction of high value-added deuterated chemicals and pharmaceuticals from low costing and easily available alcohols and ketones.

Amorphous spherically-shaped metal-organic framework (MOF) microcavities have been constructed by amorphizing MOFs with a topological distortion network through introducing flexible building blocks, which possess a Q factor as high as ≈10⁴ and can provide sufficient feedback for high-quality single-mode lasing oscillations. The results will pave an avenue for the construction of new types of flexible MOFs-based photonic components.

Simultaneous dual-channel switching of luminescence and conducting can be achieved from a simple organic crystal by UV irradiation, which is because of the sensitive and repeatable generation of photoinduced luminescent radicals inside.

A diiodo trifluoromethyl sulfur-chelated ruthenium benzylidene complex was synthesized as precatalyst for olefin metathesis, allowing ring-opening metathesis of dicyclopentadiene in the presence of a methylene donor to produce 1,3-divinyl-hexahydropentalenes and depolymerization of polybutadiene upon green light irradiation. The selectivity displayed by the catalyst is attained through a fine balance between its rate of pre-activation and deactivation.

A three-dimensional monolithic Pt/MnO₂-BN catalyst was prepared by anchoring Pt/MnO₂ nanoflower on boron nitride (BN) aerogels. The as-formed porous aerogels catalyst offers a combination of adsorption and oxidation to efficiently remove formaldehyde at room temperature, as well as easier recycling and reuse in comparison with powdery catalysts.

Selective synthesis of azobenzene compounds and azoxybenzene compounds with N=N bonds was performed by a molecular molybdenum oxide compound [N(C₄H₉)₄]₂[Mo₆O₁₉] (simplified as Mo₆) under mild conditions. A series of symmetric and asymmetric azobenzenes and azoxybenzenes were produced in high yield and selectivity by changing additive and solvent. Moreover, the catalytic mechanism of the reaction system was also assumed appropriately.

Based on first-principles and experimental studies, the design strategy from (PO₄)³⁻ to (PO₃S)³⁻ is confirmed to enhance the birefringence and second harmonic generation (SHG) effect while maintaining large band gap. The oxythiophosphate KH₂PO₃S with novel motif of (H₂PO₃S)⁻ is accordingly predicted to exhibit better UV NLO balance than KH₂PO₄, including larger birefringence, stronger SHG effect, and shorter phase-matching SHG wavelength.

Molecular NiF₃ and NiF₄ are the missing tri- and tetrafluorides of the otherwise known binary first-row transition-metal fluorides that are predicted to be stable. These elusive high-valent molecular nickel fluorides were identified in rare-gas matrices aided by high-level quantum chemical electronic structure calculations. They are among the most powerful known fluorination and oxidation agents.

Strained….in Flow! The first telescoped continuous flow protocol for the generation, lithiation, and electrophilic trapping of 1-azabicyclo[1.1.0]butane is reported. Several structurally unique C3-functionalized 1-azabicyclo[1.1.0]butanes were prepared using this strategy starting from readily available starting materials.

Triplet HCCP is produced as the final product of the UV induced rearrangement and subsequent dehydrogenation of phosphapropyne, CH₃C≡P, in solid Ar. Phosphaallene CH₂=C=PH, and ethynylphosphine, HC≡CPH₂ are produced as H atoms are transferred along the CCP skeleton prior to dehydrogenation.

Eine reiche strukturelle Vielfalt an formkomplementären, metallo-supramolekularen Strukturen wird durch die Verbrückung von Liganden über ihre Zentraleinheiten erreicht. Es konnte eine Reihe neuer heteroleptischer Gebilde erhalten werden, von dimeren Käfigen über eine prismatische Struktur bis hin zu einem Pseudotetraeder. Der Einfluss von Linker-Flexibilität, Lösungsmittel und Gastmolekülen wurde untersucht.

Die Herstellung muschelkleberinspirierter Polymere auf Basis großtechnisch verfügbarer Monomere eröffnet vielfältige Möglichkeiten. Vorgestellt wird ein chemischer Oxidationsweg über den Dichinone erhalten werden, die anschließend in Michael-Polyadditionen mit verschiedenen Dithiolen umgesetzt werden. Der modulare Ansatz ergibt eine Klebstoff-Bibliothek mit Thiol-Catechol-Haftfunktionalitäten und interessanten Unterwasser-Klebeigenschaften.

Das 1,4-Distannabenzol-Derivat 4 mit zweifach koordinierten Sn^I-Atomen wurde als grüner, kristalliner Feststoff isoliert. Der Grundzustand von 4 ist ein offenschaliges Singulett (OS) mit der Singulett-Triplett-Energielücke (ΔE_OS–T) von 4.4 kcal mol⁻¹ (nach CASSCF, ΔE_S–T=6.6 kcal mol⁻¹). Folglich zeigt 4 ein Halbfeld-EPR-Signal bei 100 K und addiert H₂-Gas bei Raumtemperatur, wobei quantitativ das Sn^II-Hydrid 5 als orangefarbener Feststoff entsteht.

Geleitet durch mechanistische Einblicke wurden elektrochemische Rhodium-katalysierte [5+2]-Cycloadditionen für den Aufbau von siebengliedrigen Benzoxepinen realisiert.

Die Metall-katalysierte Hydrierung von Aromaten ist eine effiziente Transformation, um gesättigte Carbo- und Heterocyclen zu erhalten, die allerdings auf die Bildung von C-H- und N-H-Bindungen beschränkt ist. Wir stellen hier die Synthese von enantioangereicherten δ-Lactamen aus leicht verfügbaren Oxazolidinon-substituierten Pyridinen vor. Entscheidend für diese Reaktion ist die Unterbrechung der Aromatenreduktion durch nukleophile Substitution.

Die Iod(I/III)-katalysierte Konstruktion eines enantioangereicherten fluorierten Isoster der Isopropylgruppe wird beschrieben. Die in situ Generierung einer chiralen ArIF₂-Spezies ermöglicht die Difluorierung von leicht zugänglichen α-CF₃-Styrolen, um ein Stereozentrum mit den Substituenten F, CH₂F und CF₃ aufzubauen (bis zu 95 %, >20:1 vic:gem Difluorierung). Zur Validierung der Enantioselektivität wurde eine Katalysatoroptimierung durchgeführt.

Reaktionen von (tBuCP)₂ mit N-heterocyclischen Carbenkomplexen von Nickel führen zur P-C-Bindungsspaltung und der Verknüpfung zweier (tBuCP)₂-Einheiten. Die so gebildeten Metallkomplexe weisen ungewöhnliche phosphaorganische Gerüste auf und zeigen eine bemerkenswerte Folgechemie. Die Ergebnisse zeigen, dass (tBuCP)₂ als Baustein für die Synthese ungewöhnlicher Phosphaorganometallverbindungen genutzt werden kann.

Bismutamide des Typs [Bi(NAr₂)₃] wurden synthetisiert und charakterisiert. Sie können Aminylradikale [NAr₂]^. freisetzen und durch Radikalkupplung die hochselektive Generierung von Hydrazinen [NAr₂]₂ induzieren. Zudem vermitteln sie die selektive Dehydrokupplung von HPnR₂ (Pn=N, P, As), auch von schwierig zu kuppelnden Substraten. Dabei sind die Reaktionsbedingungen, der Mechanismus und die Substratbreite komplementär zu oder günstiger als bei etablierten Methoden.

Während die Reduktion cyclischer Alkyl(amino)carben-stabilisierter Borisothiocyanate in der Gegenwart einer Lewis-Base dreifach koordinierte Isothiocyanatoborylene ergibt, liefert die Reduktion in Abwesenheit einer Lewis-Base die ersten Beispiele für intensiv blaue, Bor-dotierte, aromatische Thiazolthiazole.

Eine Te^II/Te^III-katalysierte dehydrierende C-H-Phenothiazinierung von anspruchsvollen Phenolen mit elektronenziehenden Substituenten unter milden, aeroben Bedingungen liefert hohe Ausbeuten. Diese unerwarteten Te^II/Te^III-radikalkatalytischen Eigenschaften wurden mithilfe von Cyclovoltammetrie, ESR-Spektroskopie, kinetischen Experimenten und DFT-Rechnungen untersucht.

Das Germaniummonogermanid wird durch Hochdruck- und Hochtemperatur-Synthese dargestellt. Die chemische Bindung in LuGe wird als kovalent gebundene Zickzackketten von Ge-Atomen und Lu₄-Polykationen beschrieben, die mit Hilfe „überschüssiger“ Elektronen im Sinne der Zintl-Bilanz Lu³⁺(2b)Ge²⁻ × 1 e⁻ gebildet werden. Die homonukleare Bindung in dem Polykation in LuGe ähnelt der Bindungssituation in Ga₂Se₂.

This chiral organo-osmium complex catalyses enantioselective reduction of pyruvate to lactate in cancer cells. The bromine tag on the chelated ligand and osmium have been jointly mapped in cells by X-ray fluorescence and inductively coupled plasma-mass spectrometry, revealing facile displacement of the ligand and its translocation to the nucleus.

The highly ordered coaggregates of quantum dots (QDs) with inter-QD interaction can be created by using the self-assembled azobenzene derivatives. Furthermore, the inter-QD interaction can be reversibly controlled by photoirradiation and time-aging.

¹⁵N relaxation data suggest that amino-terminal histone H4 tails in reconstituted nucleosome are flexible. This result is rationalized by suitably designed MD simulations, showing that H4 tails are involved in a fuzzy interaction with nucleosomal DNA while retaining their disordered character.

A novel osmotic pressure sensor based on liposomes loaded with FRET dyes is developed, which experience volume changes responding to osmotic pressure due to water outflux through their semipermeable membrane. With FRET microscopy, measurement of osmotic pressures in situ with spatiotemporal resolution is demonstrated, which has not been achieved so far.

We are demonstrating a new model membrane system, flat vesicles on top of a supported lipid bilayer. By reconstituting a paradigmatic biological pattern-forming system, ATP-dissipating MinDE proteins, dynamic „breathing“ deformations of the soft membrane vesicles and progressive membrane spreading are achieved, confirming that under this specific condition, MinDE reaction cycles can result in work performed on the biological membrane.

Concentration-dependent number and brightness (cdN&B) is a fluorescence fluctuation technique that can be implemented on a standard confocal microscope and report on the thermodynamics of membrane protein association in the native plasma membrane. cdN&B uses transient transfection to enable measurements of oligomer size as a function of receptor concentration over a broad range, yielding the association constant.

We propose a macromolecular-drug-induced extracellular chemotherapy involving biomineralization by absorbing calcium from blood. Polysialic acid combined with folate, which spontaneously induces biogenic mineral formation on cancer cells rich in folate receptors, leads to targeted pathological calcification and cell death. Systemic administration of folate-polySia improves survival rates of tumor-bearing mice with negligible side effects.

The intramolecular photoinduced electron transfer of a series of polyoxometalate (POM)-bodipy hybrids was examined. The data show that both solvents and counterions have a major impact on the relaxation dynamics of the excited states by modifying the solvation shell around the POM. The experimental findings were corroborated with a computational investigation combining DFT and molecular dynamics simulation methods.

A decorated zeolite material, Cu@FAU, exhibits highly selective adsorption of acetylene and thus efficient separation of acetylene and carbon dioxide, unlocking the potential of zeolite materials in challenging industrial separations.

A facile synthesis of two-dimensional coplanar Pt-carbon nanomeshes with high surface distortion has been developed. This electrocatalyst showed superior activity and stability for the oxygen reduction reaction in a fuel cell.

A method for site-directed conjugation to antibodies is developed, in which a first lysine both directs and activates the reagent for reaction with a neighboring lysine.

A dual-metal catalysis was established for the asymmetric coupling of alkoxyallenes with aldimine esters. This method resulted in the diastereodivergent synthesis of β-amino alcohol motifs. The total synthesis of mycestericins F and G was demonstrated.

A novel Turing-type Ag₂Se-CoSe₂ structure has been synthesized, which possesses rich Ag₂Se-CoSe₂ interfaces, exhibiting a 221 mV overpotential at a current density of 10 mA cm⁻² in 0.1 M KOH electrolyte with a high anodic energy efficiency of 84.5 %.

A surface functionalization strategy, utilizing Co-MOF/PDMS as tandem coating layers, was proposed to overcome the problem of humidity sensitivity for semiconducting metal-oxide-based gas sensors. This approach can be extended to various humidity-independent gas-sensing materials.

Conformational plasticity defines cell permeabilization activity: Cell permeabilization activities of cyclic Ras-inhibitor peptides are determined by the ability to adopt a cell-permeable amphipathic conformation, in which aromatic residues (green) are converged on one side and the Arg residues (blue) surround the aromatic residues, in a low polarity environment.

A drug-sponge nanocarrier that reversibly captures and releases drugs or contrast agents under pH control is developed using dynamic covalent chemistry. Inside this lipid droplet nano-reactor, lipophilic capture molecules transform free cargo-ketones into encapsulated hydrazone prodrugs, enabling the controlled release of active cargos and also their extraction from cells and tissues for detoxification.

Cancer-associated fibroblasts-responsive honeycomb-like nanoassemblies of carbon dots are fabricated to program the sequential and spatiotemporal release of multiple therapeutic agents for synergetic chemoimmunotherapy of cancer.

A protection/deprotection strategy was developed to enhance the separation performance of amine-functionalized PIM-1. Thermal deprotection yielded a synergistic boost in size-sieving and CO₂ diffusion, ultimately surpassing the H₂/CH₄, O₂/N₂ and H₂/N₂ upper bounds and boosting CO₂ permeability by 200 %.

A gradient SEI structure with C−F rich surface for strong Li⁺ adsorption and LiF rich bottom for fast Li⁺ diffusion is designed by applying bisfluoroacetamide as electrolyte additive, which also helps to form a stable CEI on cathode, endowing stable lithium metal batteries.

Single-molecule conductance of 1,4-azaborine acene-type compounds was studied using the scanning tunneling microscope break-junction technique. This substitution ensures an unambiguous electron path through both heteroatoms. A moderate change in conductance is observed when compared to the parent all-carbon structure. State-of-the-art transport calculations support the experimental results.

Cucurbiturils can be prime components to build energy ratchets in water. Guest molecules can be exchanged in the synthetic macrocycle cucurbit[7]uril by involving kinetic traps, and in such a way as modulating energy wells and kinetic barriers using pH, light, and redox stimuli

A DNA intercalator, K21, can form transient excimers on the surface of DNA. The ratiometric emission of monomer and excimer was strongly correlated to DNA transient conformation stability. The K21 excimer can probe transient DNA conformation changes in DNA structures with various length and shape. This label-free method can also probe the transient conformation change in single plasmid under supercoiled and open-circular states.

The dual catalytic role of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was revealed for the aerobic α-hydroxylation of ketones under a metal- and phosphine-free method. By means of a double-proton-transfer process, TBD activates the α-C(sp³)−H bond of ketones, avoiding the necessity of an alkali metal. Most importantly, TBD enhances the activity of the peroxide intermediate through the double hydrogen bonds, allowing reduction by DMSO in the absence of a phosphine reductant.

A self-resistance mechanism involving a cycle of extracellular oxidative activation and intracellular reductive inactivation was revealed by identifying the biosynthesis pathway of the macrolide antibiotic A26771B (1). This finding not only expands the understanding of resistance toward macrolide antibiotics, but also guides efforts to develop new antibiotics.

A cooperative strategy for stapling native peptides at lysine and nearby tyrosine or arginine residues with formaldehyde is reported.

Piptides, a new form of chemotype, are accessible from natural amino acids in either configuration, hence can conveniently display all the side chain pharmacophores found in peptides and proteins. They can be made in solution or on supports and are proteolytically-/pH-robust. Piptide-based disruption of EGF⋅EGFR was chosen as an initial challenge and Exploring Key Orientations (EKO) was used to evaluate candidates.

Catalytic C−H methylation proceeds efficiently under solvent-free, mechanochemical conditions, including the late-stage functionalization of biologically active substrates and otherwise difficult-to-make metalacyclic complexes.

Ligand-capped PbS colloidal nanoparticles grow by liquid-like coalescence rather than Ostwald ripening in the absence of supersaturation. The effective activation energy of the coalescence process is associated with two factors: one is proportional to the contact area between the ligand shells of two colliding particles and the other is related to the reconstruction. The model successfully predicts the growth kinetics of nanoparticles.

2D porous MoP/Mo₂N heterojunction nanosheets have been created based on a PEG-mediated assembly strategy, which exhibit outstanding performance for HER over wide pH ranges even out-performing the Pt/C benchmark at large current density. A series of tests and DFT calculations shows the synergy of the heterojunctions, pores and 2D nanosheets for promoting the HER performance.

Unprecedented low-coordinate carbodicarbene bismaalkene cations have been prepared which feature C Bi double dative bonds. The synthesis of these compounds represents a unique non-reductive route to C=Bi double-bond character.

The [FeO₆] polyhedral hydration structure of ferrihydrite is responsible for its hole storage function. With the continuous loss of three molecules of crystal water, the quantity of stored photogenerated holes for PEC water oxidation gradually decreases, accompanied by the destruction of the hydration structure.

The combination of chloride and alkynyl as protecting agents leads to the formation of large gold nanoclusters. Silica gel column chromatography results in the successful isolation and crystallization of atomically precise gold nanoclusters [HNEt₃]₃[Au₆₇L₃₂Cl₄] (Au₆₇), [HNEt₃]₄[Au₁₀₆L₄₀Cl₁₂] (Au₁₀₆), where L=3,5-bis(trifluoromethyl)-phenylacetylide. They are all superatomic clusters, and show size-dependent electrochemical properties.

Cancer stem cells (CSCs) are associated to cancer relapse and metastasis. Herein, the breast CSC activities of Group 10-bis(azadiphosphine) complexes under exclusively three-dimensional cell culture conditions, are systematically compared. Breast CSC mammosphere inhibition and potency was highly dependent on the Group 10 metal present.

The energetic differences for the glycolysis of BPA-PC and PET in the presence of a protic ionic salt TBD:MSA catalyst enable the selective and sequential depolymerisation of these two commonly employed polymers. Functionalised cyclic carbonates can be obtained from both mixed plastic wastes and industrial polymer blend.

Superionic halide solid electrolytes show excellent cathodic electrolyte properties in solid state batteries, but they are unstable in contact with the lithium metal anode. The forming solid electrolyte interphase is analyzed herein, using X-ray photoelectron spectroscopy and impedance spectroscopy. Additionally, the hetero-interface between Li₃InCl₆ and Li₆PS₅Cl is analyzed to highlight the concept of hybrid electrolyte cells.

A dipeptide hydrogel was obtained by dynamic assembly in the confined space of continuous-flow microfluidics. Organic porphyrins and inorganic quantum dots (QDs) were integrated in the system for energy transfer, and dynamic structural control over hydrogel formation and QD integration occurred within the microchannel network (see picture).

An intelligent molecular-lock device of signaling ligand proteins, termed „scan and unlock“ DNA automaton (SUDA), is presented. The SUDA employs DNA chemical reaction networks to autonomously scan and logically evaluate the cell-surface-protein profile of the designated cell type, selectively unlocking the signaling ligand–receptor interactions for cell-specific signaling.

An achiral supramolecular organic framework (SOF) exhibits adaptive chirality with dual circular dichroism and circularly polarized luminescence responses when meeting various chiral guests, including L-/D-Phe, adenosine derivatives, and peptides/proteins via chirality induction in water. The adaptive chirality of the SOF can be used as a chiroptical platform to determine the enantiopurity, develop aqueous CPL materials, and distinguish peptides/proteins.

A highly reactive S=2 pseudotetrahedral oxoiron(IV) complex 2 supported by a sterically demanding 1,4,7-tri-tert-butyl-1,4,7-triazacyclononane ligand has been synthesized and spectroscopically characterized as one of the best electronic and functional models for a biological oxoiron(IV) intermediate of taurine dioxygenase (TauD-J).

A P/B-H frustrated Lewis pair is formed by means of a rare 1,1-hydroboration reaction. It reacts in an unusual way with a variety of organic π-systems by addition/rearrangement routes.

Small, photoswitchable (MW 258 g mol⁻¹) arylazopyrazoles form self-assembled gels in water that can be reversibly cycled between a gel and solution state using two different excitation wavelengths that cause „thinning“ of the gel fibers upon the light induced E to Z isomerisation. These materials could be used for light-controlled cargo release.

Neue Bausteine für gemischtvalente Ladungstransferverbindungen: Planare N-Heterotriangulendimere mit geringer Reorganisationsenergie und Aktivierungsbarriere für Elektronenselbstaustausch wurden synthetisiert und untersucht.

Ylid-funktionalisierte Phosphane wurden für die Anforderungen von Negishi-Kupplungen von Arylchloriden bei Raumtemperatur maßgeschneidert. Der YPhos/Pd-Katalysator ist hocheffizient für die Kupplung mit Arylchloriden im Allgemeinen, und die Reaktion zeigt eine ausgezeichnete Kompatibilität gegenüber funktionellen Gruppen. Dies ermöglicht die selektive Kupplung von Arylelektrophilen in konkurrierenden Reaktionen, wie bei der Synthese von Ibuprofen demonstriert.

LGa reagiert mit einem Gallaphosphaketen zum Gallaphosphen L(Cl)GaPGaL, das nach Halogenidabstraktionsreaktion das Heteroallylkation [LGaPGaL]⁺ ergibt. L(Cl)GaPGaL reagiert außerdem reversibel mit CO₂ und selektiv unter C(sp³)-H-Bindungsaktivierung mit Acetophenon und Aceton.

Der durch Hydrierung mit Parawasserstoff erzeugte ¹H-Singulettzustand von Fumarate wird durch enzymatische Konversion in Malat umgewandelt, was die hyperpolarisierten NMR-Signale freisetzt. Wir demonstrieren zwei „Out-of-Phase Echo“ Pulssequenzen die den I_1zI_2z Zustand in ¹H-Nettomagnetisierung umwandeln und zeigen die Anwendung in der hyperpolarisierten ¹H-Bildgebung.

Die Feinabstimmung der Ligandenstruktur ermöglicht es, chemische Sonden schnell auf Wirksamkeit und Spezifität für das aktive Zentrum von Proteasen zuzuschneiden. Eine Anwendung zur Ligandenselektion wird durch die Entwicklung von Sonden für die beiden nicht homologen, aber essentiellen Proteasen von SARS-CoV-2 demonstriert, womit komplementäre chemische Werkzeuge für die proteomische Markierung und die Entdeckung von Inhibitoren verfügbar gemacht werden.

Die quantitative Umwandlung von HMF zu DMF wurde in Gegenwart von Ameisensäure und H₂ über dem bifunktionellen Pd/NMC-Katalysator innerhalb von 2 h erreicht. Experimentelle Untersuchungen und DFT-Berechnungen ergaben, dass Ameisensäure die Reaktionsgeschwindigkeit deutlich erhöht und den dominanten Reaktionsweg von der Hydrierung der Aldehydgruppe zur Hydrogenolyse der Hydroxymethylgruppe über deren Protonierung verschiebt.

Doppelhelikales 1D-SnIP und 2D-Phosphoren entstehen in einer Gasphasenreaktion aus weißem Phosphor (P₄) und SnI₂. Mittels P₄-Aktivierung wird das Helix-Wachstum oder die Phosphorenbildung initiiert. Sn₂I₄-Dimere koordinieren die freien Elektronenpaare des Phosphors beim SnIP, während eine direkte Sn-Insertion in die P-P-Bindung zur Phosphorenbildung führt. Beide Reaktionswege werden zwischen 0 K und den jeweiligen Synthesetemperaturen beleuchtet.