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.

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.

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.

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.

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.

Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands.

Compounds containing Mn-O bonds are of utmost importance in biological systems and catalytic processes. Nevertheless, mononuclear manganese complexes containing all O-donor ligands are still rare. Taking advantage of the low tendency of the pentafluoroorthotellurate ligand (teflate, OTeF) to bridge metal centers, we have synthesized two homoleptic manganese complexes with monomeric structures and an all O-donor coordination sphere.

A Highly Sterically Encumbered Boron Lewis Acid Enabled by an Organotellurium-Based Ligand.

Lewis acidic boron compounds are ubiquitous in chemistry due to their numerous applications, yet tuning and optimizing their properties towards different purposes is still a challenging field of research. In this work, the boron-based Lewis acid B[OTeF(CF)] was synthesized by reaction of the teflate derivative HOTeF(CF) with BCl or BCl ⋅ SMe. This new compound presents a remarkably high thermal stability up to 300 °C, as well as one of the most sterically encumbered boron centres known in the literature.

Generation and Identification of the Trifluorosilylarsinidene FSiAs and Isomeric Perfluorinated Arsasilene FAsSiF.

The trifluorosilylarsinidene FSiAs in the triplet ground state has been generated through the reaction of laser-ablated silicon atoms with AsF in cryogenic Ne- and Ar-matrices. The reactions proceed with the initial formation of perfluorinated arsasilene FAsSiF in the singlet ground state by two As-F bonds insertion reaction on annealing. The trifluorosilylarsinidene FSiAs was formed via F-migration reactions of FAsSiF under irradiation at UV light (λ = 275 nm).

Investigation of Isolated IrF , IrF Anions and M[IrF] (M=Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations.

The molecular IrF , IrF anions and M[IrF] (M=Na, K, Rb, Cs) ion pairs were prepared by co-deposition of laser-ablated alkali metal fluorides MF with IrF and isolated in solid neon or argon matrices under cryogenic conditions. The free anions were obtained as well by co-deposition of IrF with laser-ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for spin-orbit coupling (SOC) effects as well as multi-reference configuration-interaction (MRCI) approaches with SOC.

Silver(i) Perfluoroalcoholates: Synthesis, Structure, and their Use as Transfer Reagents.

Herein we report a general access to silver(i) perfluoroalcoholates, their structure in the solid state and in solution, and their use as transfer reagents. The silver(i) perfluoroalcoholates are prepared by the reaction of AgF with the corresponding perfluorinated carbonyl compounds in acetonitrile and are stable for a prolonged time at -18 °C. X-ray analysis of single crystals of perfluoroalcoholate species showed that two Ag(i) centers are bridged by the alcoholate ligands.

Spectroscopic Identification of Trifluorosilylphosphinidene and Isomeric Phosphasilene and Silicon Trifluorophosphine Complex.

The perfluorinated silylphosphinidene, FSiP, in the triplet ground state is generated by the reaction of laser-ablated silicon atoms with PF in solid neon and argon matrices. The reactions proceed with the initial formation of a silicon trifluorophosphine complex, FPSi, in the triplet ground state, and a more stable inserted phosphasilene, FPSiF, in the singlet ground state upon deposition. The trifluorosilylphosphinidene was formed through F-migration reactions of FPSiF and FPSi following a two-state mechanism under irradiation with visible light (λ = 470 nm) and full arc light (λ > 220 nm), respectively.

Bichloride-based ionic liquids for the merged storage, processing, and electrolysis of hydrogen chloride.

Hydrogen chloride is produced as a by-product in industrial processes on a million-ton scale. Since HCl is inherently dangerous, its storage and transport are avoided by, e.g.

Formation of Peroxynitrite, [O-N-O-O], via a Cascade of Reactions between Ozonide and Ammonia.

We report on an unexpected reaction between ammonia and potassium ozonide dissolved in liq. NH resulting in the formation of peroxynitrite, [ONOO], which exclusively happens in the presence of a specific partially fluorinated aniline-based ammonium cation. High-resolution structural data of the peroxynitrite anion in cis-conformation have been obtained.