GATA2 links stemness to chemotherapy resistance in acute myeloid leukemia.

Stemness-associated cell states are linked to chemotherapy resistance in AML. We uncovered a direct mechanistic link between expression of the stem cell transcription factor GATA2 and drug resistance. The GATA-binding protein 2 (GATA2) plays a central role in blood stem cell generation and maintenance.

Halogenated Trityl Cations as Easy-to-Access Super Electrophiles.

Herein, we present the easy-to-access synthesis of the perfluorotrityl cation (15F) with commercial GaCl and the further functionalization of the para-fluorine atoms of 15F via halodefluorination using trimethylsilyl halides TMSX (X=Cl, Br). This gives access to equally reactive halogenated trityl derivatives (p-3Cl12F and p-3Br12F), which can be handled at room temperature. The impact of the para-exchange on the electronic structure is determined by NMR and UV/Vis spectroscopy.

Polyethyleneimine-Based Cryogels Enabling the Selective and Reversible Adsorption of Chlorine.

Herein hyperbranched polyethyleneimine (hPEI) cryogels are reported for the selective and reversible adsorption of elemental chlorine. The cryogels are prepared in an aqueous solution by crosslinking with glutaraldehyde at subzero temperatures. The final macroporous composites bearing ammonium chloride groups are obtained after freeze-drying.

Polyhydroxykanoate-Assisted Photocatalytic TiO Films for Hydrogen Production.

The photocatalytic production of hydrogen using biopolymer-immobilized titanium dioxide (TiO) is an innovative and sustainable approach to renewable energy generation. TiO, a well-known photocatalyst, benefits from immobilization on biopolymers due to its environmental friendliness, abundance, and biodegradability. In another way, to boost the efficiency of TiO, its surface properties can be modified by incorporating co-catalysts like platinum (Pt) to improve charge separation.

Influence of Chloride and Electrolyte Stability on Passivation Layer Evolution at the Negative Electrode of Mg Batteries Revealed by operando EQCM-D.

Rechargeable magnesium batteries are promising for future energy storage. However, among other challenges, their practical application is hindered by low coulombic efficiencies of magnesium plating and stripping. Fundamental processes such as the formation, structure, and stability of passivation layers and the influence of different electrolyte components on them are still not fully understood.

Dichlorine-pyridine -oxide halogen-bonded complexes.

A new Cl-Cl···O-N halogen-bonded paradigm has been demonstrated, using dichlorine as a halogen bond (XB) donor and -oxide as an XB acceptor. Their crystalline complexes were formed during the warm-up process from -196 °C to -80 °C for X-ray diffraction analysis. They exhibit high instability in the crystalline state, even at these low temperatures, leading to rapid decomposition and the formation of Cl⋯H-O-N hydrogen-bonded complexes.

A polychloride-enabled synthesis of [NEtMe][PCl] serving as a potential PCl-storage and PCl-reagent.

Reaction of the ionic liquid [NEtMe][Cl] with white phosphorus (P) gives, quantitatively, hexachlorophosphate [NEtMe][PCl]. This compound shows similar reactivity as PCl, as confirmed for the reaction with phenol, carboxylic acids and ammonium chloride. At elevated temperature, [NEtMe][PCl] releases PCl and can therefore be used as a potential PCl-storage material.

The Trifluorooxygenate Anion [OF]: Spectroscopic Evidence for a Binary, Hypervalent Oxygen Species.

Experimental evidence for hypervalent compounds of second-row elements is still scarce in literature. Here, we present the first report of the long-sought binary, hypervalent trifluorooxygenate anion [OF]. It was isolated in solid Ne matrices under cryogenic conditions after reacting oxygen difluoride with free fluoride ions from laser ablation of alkali metal fluorides MF (M=Li-Cs).

Streamlining Thionyl Tetrafluoride (SOF) and Pentafluoro-Oxosulfate [OSF] Anions Syntheses.

A one pot room temperature synthesis of thionyl tetrafluoride (SOF) from elemental fluorine (F) and thionyl fluoride (SOF) is reported. The selective decagram scale process (100 mmol) allows a quantitative preparation of SOF with high purity. The solid-state structure has also been elucidated and compared with the reported gas phase one.

A Rare Example of a Gallium-Based Lewis Superacid: Synthesis and Reactivity of Ga(OTeF).

The Lewis superacid Ga(OTeF) has been synthesized and characterized, revealing a monomeric structure in solution and a dimeric structure in the solid state. Isolated adducts of Ga(OTeF) with strong and weak Lewis bases have been characterized spectroscopically as well as by single-crystal X-ray diffractometry. The Lewis acidity of this new species has been evaluated by means of different experimental and theoretical methods, which has allowed to classify it as one of only a few examples of a gallium-based Lewis superacid.

Synthetic biology toolkit of Ralstonia eutropha (Cupriavidus necator).

Synthetic biology encompasses many kinds of ideas and techniques with the common theme of creating something novel. The industrially relevant microorganism, Ralstonia eutropha (also known as Cupriavidus necator), has long been a subject of metabolic engineering efforts to either enhance a product it naturally makes (polyhydroxyalkanoate) or produce novel bioproducts (e.g.

Recent Advances in Electrolytes for Magnesium Batteries: Bridging the gap between Chemistry and Electrochemistry.

Rechargeable magnesium batteries (RMBs) have the potential to provide a sustainable and long-term solution for large-scale energy storage due to high theoretical capacity of magnesium (Mg) metal as an anode, its competitive redox potential (Mg/Mg:-2.37 V vs. SHE) and high natural abundance.

Oxygen Atom Stabilization by a Main-Group Lewis Acid: Observation and Characterization of an OBeF Complex with a Triplet Ground State.

Terminal oxygen radicals involving p- and d-block atoms are quite common, but s-block compounds with an oxygen radical character remain rare. Here, we report that alkaline-earth metal beryllium atoms react with OF to form the oxygen beryllium fluorides OBeF and OBeF. These species are characterized by matrix-isolation infrared spectroscopy with isotopic substitution and quantum-chemical calculations.

Fluorinated Dialkyl Chloronium Salts: Synthesis and Reactivity for Fluoroalkylation and Hydride Abstraction.

A new concept for the synthesis of dialkyl chloronium cations [R-Cl-R] is described (R=CH, CHCF), that allows the formation of fluorinated derivatives. By utilizing the xenonium salt [XeOTeF][M(OTeF)] (M=Sb, n=6; M=Al, n=4) chlorine atoms of chloroalkanes or the deactivated chlorofluoroalkane CHClCF are oxidized and removed as ClOTeF leading to the isolation of the corresponding chloronium salt. Since the resulting highly electrophilic cation [Cl(CHCF)] is able to alkylate weak nucleophiles, this compound can be utilized for the introduction of a fluorinated alkyl group to those.

Designing highly efficient interlocking interactions in anisotropic active particles.

Cluster formation of microscopic swimmers is key to the formation of biofilms and colonies, efficient motion and nutrient uptake, but, in the absence of other interactions, requires high swimmer concentrations to occur. Here we experimentally and numerically show that cluster formation can be dramatically enhanced by an anisotropic swimmer shape. We analyze a class of model microswimmers with a shape that can be continuously tuned from spherical to bent and straight rods.

Elucidating regulation of polyhydroxyalkanoate metabolism in Ralstonia eutropha: Identification of transcriptional regulators from phasin and depolymerase genes.

Despite the ever-growing research interest in polyhydroxyalkanoates (PHAs) as green plastic alternatives, our understanding of the regulatory mechanisms governing PHA synthesis, storage, and degradation in the model organism Ralstonia eutropha remains limited. Given its importance for central carbon metabolism, PHA homeostasis is probably controlled by a complex network of transcriptional regulators. Understanding this fine-tuning is the key for developing improved PHA production strains thereby boosting the application of PHAs.

Porous Azatruxene Covalent Organic Frameworks for Anion Insertion in Battery Cells.

Covalent organic frameworks (COFs) containing well-defined redox-active groups have become competitive materials for next-generation batteries. Although high potentials and rate performance can be expected, only a few examples of p-type COFs have been reported for charge storage to date with even fewer examples on the use of COFs in multivalent ion batteries. Herein, we report the synthesis of a p-type highly porous and crystalline azatruxene-based COF and its application as a positive electrode material in Li- and Mg-based batteries.

High-cell-density fed-batch strategy to manufacture tailor-made P(HB-co-HHx) by engineered Ralstonia eutropha at laboratory scale and pilot scale.

The transition towards a sustainable bioeconomy requires the development of highly efficient bioprocesses that enable the production of bulk materials at a competitive price. This is particularly crucial for driving the commercialization of polyhydroxyalkanoates (PHAs) as biobased and biodegradable plastic substitutes. Among these, the copolymer poly(hydroxybutyrate-co-hydroxyhexanoate) (P(HB-co-HHx)) shows excellent material properties that can be tuned by regulating its monomer composition.

Introducing AFS ([Al(SOF)]) - a thermally stable, readily available, and catalytically active solid Lewis superacid.

Common Lewis superacids often suffer from low thermal stability or complicated synthetic protocols, requiring multi-step procedures and expensive starting materials. This prevents their large-scale application. Herein, the easy and comparably cheap synthesis of high-purity aluminium tris(fluorosulfate) ([Al(SOF)], AFS) is presented.

B[double bond, length as m-dash]P double bonds relieved from steric encumbrance: matrix-isolation infrared spectroscopy of the phosphaborene FB-P[double bond, length as m-dash]BF and the triradical B[double bond, length as m-dash]PF.

Free phosphaborenes have a labile boron-phosphorus double bond and therefore require extensive steric shielding by bulky substituents to prevent isomerisation and oligomerisation. In the present work, the small free phosphaborene FB-P[double bond, length as m-dash]BF was isolated by matrix-isolation techniques and was characterised by infrared spectroscopy in conjunction with quantum-chemical methods. In contrast to its sterically hindered relatives, this small phosphaborene exhibits an acute BPB angle of 83° at the CCSD(T) level.

N cleavage by silylene and formation of HSi(μ-N)SiH.

Fixation and functionalisation of N by main-group elements has remained scarce. Herein, we report a fixation and cleavage of the N ≡ N triple bond achieved in a dinitrogen (N) matrix by the reaction of hydrogen and laser-ablated silicon atoms. The four-membered heterocycle HSi(μ-N)SiH, the HSiNN(H) and HNSiNH complexes are characterized by infrared spectroscopy in conjunction with quantum-chemical calculations.