Enantioselective C-H amination catalyzed by homoleptic iron salox complexes.

Iron complexes bearing chiral salicyloxazoline (Salox) ligands catalyze the enantioselective intramolecular C-H bond amination of alkyl azides, reaching 58-76% ee for benzylic C-H bonds. Further, for the first time aliphatic C-H bond amination is demonstrated (∼40% ee). This class of catalysts even activates primary aliphatic C-H bonds, albeit with moderate ee.

Ligand modification for the tuning of activity and selectivity in the chemoselective transfer hydrogenation of α,β-unsaturated carbonyls using EtOH as a hydrogen source.

The selective reduction of α,β-unsaturated ketones, either at the olefinic or the carbonyl site, offers attractive synthetic opportunities. While carbonyl reduction is well established, selective olefin reduction is less common, particularly when using environmentally friendly ethanol as a hydrogen source. Recently, we reported a coordinatively unsaturated ruthenium complex containing an ,'-bidentate coordinating pyridinium amidate (PYA) ligand as an efficient catalyst for ethanol-based transfer hydrogenation of α,β-unsaturated ketones; however, there was over-reduction and thus loss of selectivity in reactions over an extended period of time.

Epitaxial Growth of CaTiO Thin Films by Metal Organic Vapor Phase Epitaxy for Potential Applications in Memristive Devices.

Calcium titanate thin films with high structural quality were grown heteroepitaxially on perovskite oxide substrates using the liquid-delivery spin metal-organic vapor phase epitaxy (MOVPE) technique. To determine the growth window, suitable metal-organic precursors were selected, and their evaporation conditions were established. Initially, the thermal decomposition behavior of the precursors was studied using thermogravimetric analysis, which showed that full pyrolysis at 460 °C is possible for both the Ca and Ti precursors.

Transcriptomic characterization of GMP-compliant regulatory macrophages (TRI-001) under inflammatory and hypoxic conditions: a comparative analysis across macrophage subtypes.

Background: Regulatory macrophages (Mreg) represent a unique subset of macrophages known for their angiogenic and anti-inflammatory properties, positioning them as promising candidates for cell-based therapies. Recently, we have differentiated and characterized a distinct Mreg subtype (TRI-001), which is currently being produced in accordance with good manufacturing practice (GMP) for a multicenter study aimed at treating patients with peripheral arterial occlusive disease (PAOD).

Aim Of The Study: To compare the transcriptome of TRI-001 with various in vitro differentiated macrophage subtypes to provide a comprehensive context for TRI-001 within the macrophage landscape.

The crucial role of acetonitrile in the mechanism of Pd(II)-catalyzed activation of polar vinyl monomers.

The migratory insertion reaction of a polar vinyl monomer into the Pd-alkyl bond and the chain walking process are two of the key steps in the catalytic cycle for the synthesis of functionalized polyolefins through coordination/insertion polymerization. Here, we present a detailed NMR investigation to gain insight into these fundamental steps and demonstrate the critical role of traces of MeCN in this process. We used Pd(II) complexes containing a N-N' bidentate pyridyl-pyridylidene amide (py-PYA) ligand, which are known to cooligomerize ethylene and methyl acrylate (MA).

Enhanced Nanoscale Ge Concentration Oscillations in Si/SiGe Quantum Well through Controlled Segregation.

The integration of electron spin qubits on Si/SiGe heterostructures requires precise control of valley splitting associated with conduction band degeneracy. This can be achieved by introducing nanoscale oscillating Ge concentration profiles, known as Wiggle Wells. However, the intermixing and segregation of Ge during growth have hindered their realization.

Enhancing activity and selectivity of palladium catalysts in ketone α-arylation by tailoring the imine chelate of pyridinium amidate (PYA) ligands.

Even though α-arylation of ketones is attractive for direct C-H functionalization of organic substrates, the method largely relies on phosphine-ligated palladium complexes. Only recently, efforts have focused on developing nitrogen-based ligands as a more sustainable alternative to phosphines, with pyridine-functionalized pyridinium amidate (pyr-PYA) ,'-bidentate ligands displaying good selectivity and activity. Here, we report on a second generation set of catalyst precursors that feature a 5-membered N-heterocycle instead of a pyridine as chelating unit of the PYA ligand to provide less steric congestion for the rate-limiting transmetalation of the enolate.

Enabling 2D Electron Gas with High Room-Temperature Electron Mobility Exceeding 100 cm Vs at a Perovskite Oxide Interface.

In perovskite oxide heterostructures, bulk functional properties coexist with emergent physical phenomena at epitaxial interfaces. Notably, charge transfer at the interface between two insulating oxide layers can lead to the formation of a 2D electron gas (2DEG) with possible applications in, e.g.

Heteroleptic Triazole-Bisoxazoline Iron Complexes Reveal Lability of the Iron-Carbene Bond Even Within a Chelating Scaffold.

N-Heterocyclic carbenes have proven to be excellent ligands for transition metals, with numerous applications in catalysis and beyond. However, they have also displayed lability with first row transition metals, largely due to the hard-soft mismatch of the metal-carbon bond. Chelation is often considered a suitable methodology for supporting the labile M-C bond through the introduction of a strongly coordinating donor site such as hard phenolates.

Tailoring C-H amination activity modification of the triazole-derived carbene ligand.

Two new C,O-bidentate chelating triazolylidene-phenolate ligands were synthesized that feature a diisopropylphenyl (dipp) and an adamantyl (Ad) substituent respectively on the triazole scaffold. Subsequent metalation afforded iron(II) complexes [Fe(C^O)] that are active catalysts for the intramolecular C-H amination of organic azides. When compared to the parent complex containing a triazolylidene with a mesityl substituent (Mes) the increased steric bulk led to slightly lower activity (TOF = 23 h 30 h), however selectivity towards pyrrolidine formation increases from 92% up to >99%.

Clinical efficacy of a multilamellar cream on skin physiology and microbiome in an epidermal stress model: A controlled double-blinded study.

Introduction: Stratum corneum (SC) is essential for skin barrier function, mitigating water loss and shielding against potentially harmful substances and allergens. The SC's lipid matrix, arranged in a lamellar structure, is integral to its protective role. Our study explores the restoration effects of a multilamellar cream with an acidic pH compared to a basic placebo cream on skin physiology and its interaction with the skin microbiome after stress induction via tape stripping (TS).

Impact of multilamellar formulations on stratum corneum lipid organization and epidermal lipid barrier enhancement (Part II).

Introduction: The integrity of the stratum corneum (SC) is crucial for the skin's barrier function, protecting against environmental stressors and minimizing transepidermal water loss. Advances in skincare formulations have introduced multilamellar systems designed to emulate the SC's lipid composition and organization. This study hypothesizes that the application of a multilamellar cream will significantly impact the SC's lipid content and lamellar structure, thereby enhancing the epidermal barrier.

Optimal Chest Compression Point During Pediatric Resuscitation: Implications for Pediatric Resuscitation Practice by CT Scans.

Objectives: Current European guidelines for pediatric cardiopulmonary resuscitation (CPR) recommend the lower half of the sternum as the chest compression point (CP). In this study, we have used thoracic CT scans to evaluate recommended and optimal CP in relation to cardiac anatomy and structure.

Design: Analysis of routinely acquired thoracic CT scans acquired from 2000 to 2020.

Effects of temporal IFNγ exposure on macrophage phenotype and secretory profile: exploring GMP-Compliant production of a novel subtype of regulatory macrophages (Mreg) for potential cell therapeutic applications.

Background: Macrophages are involved in tissue homeostasis, angiogenesis and immunomodulation. Proangiogenic and anti-inflammatory macrophages (regulatory macrophages, Mreg) can be differentiated in-vitro from CD14 monocytes by using a defined cell culture medium and a stimulus of IFNγ.

Aim Of The Study: To scrutinize the potential impact of temporal IFNγ exposure on macrophage differentiation as such exposure may lead to the emergence of a distinct and novel macrophage subtype.

Application of first-row transition metal complexes bearing 1,2,3-triazolylidene ligands in catalysis and beyond.

Triazole-derived N-heterocyclic carbenes, triazolylidenes (trz) have become an interesting alternative to the ubiquitous Arduengo-type imidazole-derived carbenes, in part because they are stronger donors, and in other parts due to their versatile synthesis through different types of click reactions. While the use of trz ligands has initially focused on their coordination to precious metals for catalytic applications, the recent past has seen a growing interest in their impact on first-row transition metals. Coordination of trz ligands to such 3d metals is more challenging due to the orbital mismatch between the carbene and the 3d metal center, which also affects the stability of such complexes.

Stable CAAC-Triazenes: A New Nitrogen Ligand System With Donor and Conformational Flexibility, and With Application in Olefin Activation Catalysis.

N-heterocyclic imines such as pyridylidene amines impart high catalytic activity when coordinated to a transition metal, largely imposed by their electronic flexibility. Here, this donor flexibility has been applied for the first time to CAAC-based systems through the synthesis of CAAC-triazenes. These new ligands offer a larger π-conjugation that extends from the N-heterocyclic carbene through three nitrogens rather than just one, as observed in N-heterocyclic imines.

From C-H to C-N Bonds: Three Challenges, Three Catalysts, Three Solutions.

N-heterocycles are key building blocks for many pharmaceutical products. An efficient and sustainable method for the synthesis of this class of compounds consists of the recently established intramolecular C-H amination reaction. Development of new iron-based catalysts for this transformation is of paramount importance.

National and International Comparisons of Gynecological Research in Germany Based on a Bibliometric Analysis of Publications.

Background: Recent years have seen a considerable shift from male doctors to female doctors in the field of gynecology. Female doctors are traditionally more involved with planning and maintaining their family. For gynecology, this could be associated with a risk that research activities will decrease, particularly if results are published in scientific journals.

Examining confidential wholesale margin estimates in European countries for the price negotiation of patented drugs in Germany: a statistical model.

Background: Based on the legal framework laid down in section 130b (9) of Book V of the German Social Code, various criteria are relevant for the negotiated price for new patented drugs in Germany. European reference prices (ERPs) are one criterion. The ERP is based on the ex-factory prices (EFPs) of the countries included in the European country basket.

Molecular Beam Epitaxy of β-(InGa)O on β-GaO (010): Compositional Control, Layer Quality, Anisotropic Strain Relaxation, and Prospects for Two-Dimensional Electron Gas Confinement.

In this work, we investigate the growth of monoclinic β-(InGa)O alloys on top of (010) β-GaO substrates via plasma-assisted molecular beam epitaxy. In particular, using different (reflection high-energy electron diffraction) and (atomic force microscopy, X-ray diffraction, time-of-flight secondary ion mass spectrometry, and transmission electron microscopy) characterization techniques, we discuss (i) the growth parameters that allow for In incorporation and (ii) the obtainable structural quality of the deposited layers as a function of the alloy composition. In particular, we give experimental evidence of the possibility of coherently growing (010) β-(InGa)O layers on β-GaO with good structural quality for up to ≈ 0.

Air-Stable Coordinatively Unsaturated Ruthenium(II) Complex for Ligand Binding and Catalytic Transfer Hydrogenation of Ketones from Ethanol.

Coordinatively unsaturated complexes are interesting from a fundamental level for their formally empty coordination site and, in particular, from a catalytic perspective as they provide opportunities for substrate binding and transformation. Here, we describe the synthesis of a novel underligated ruthenium complex [Ru(cym)(N,N')], , featuring an amide-functionalized pyridylidene amide (PYA) as the ,-bidentate coordinating ligand. In contrast to previously investigated underligated complexes, complex offers potential for dynamic modifications, thanks to the flexible donor properties of the PYA ligand.

Empagliflozin prevents oxidative stress in human coronary artery endothelial cells via the NHE/PKC/NOX axis.

Background: Empagliflozin (EMPA) ameliorates reactive oxygen species (ROS) generation in human endothelial cells (ECs) exposed to 10 % stretch, but the underlying mechanisms are still unclear. Pathological stretch is supposed to stimulate protein kinase C (PKC) by increasing intracellular calcium (Ca), therefore activating nicotinamide adenine dinucleotide phosphate oxidase (NOX) and promoting ROS production in human ECs. We hypothesized that EMPA inhibits stretch-induced NOX activation and ROS generation through preventing PKC activation.

Efficient additive-free formic acid dehydrogenation with a NNN-ruthenium complex.

A new ruthenium complex containing a pyridylidene amine-based NNN ligand was developed as a catalyst precursor for formic acid dehydrogenation, which, as a rare example, does not require basic additives to display high activity (TOF ∼10 000 h). Conveniently, the complex is air-stable, but sensitive to light. Mechanistic investigations using UV-vis and NMR spectroscopic monitoring correlated with gas evolution profiles indicate rapid and reversible protonation of the central nitrogen of the NNN ligand as key step of catalyst activation, followed by an associative step for formic acid dehydrogenation.

Draft genomes of 3 cyanobacteria strains and 17 co-habiting proteobacteria assembled from metagenomes.

and are prominent, globally distributed cyanobacteria genera with ecological significance. Here, we report the genomes of the marine sp. CCMP836 and two strains of (CZS25K and CZS48M) along with the genomes of 17 co-occurring proteobacteria.

Deciphering Iron-Catalyzed C-H Amination with Organic Azides: N Cleavage from a Stable Organoazide Complex.

Catalytic C-N bond formation by direct activation of C-H bonds offers wide synthetic potential. En route to C-H amination, complexes with organic azides are critical precursors towards the reactive nitrene intermediate. Despite their relevance, α-N coordinated organoazide complexes are scarce in general, and elusive with iron, although iron complexes are by far the most active catalysts for C-H amination with organoazides.