π-Lewis Base Activation of Carbonyls and Hexafluorobenzene.

We report hitherto elusive side-on η-bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexafluorobenzene) palladium(0) complexes and present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine and tetrahydrofuran complexes reveals that the experimental ligand binding strengths follow the order THF View Article and Find Full Text PDF

Fine-tuning of Fgf8 morphogen gradient by heparan sulfate proteoglycans in the extracellular matrix.

Embryonic development is orchestrated by the action of morphogens, which spread out from a local source and activate, in a field of target cells, different cellular programs based on their concentration gradient. Fibroblast growth factor 8 (Fgf8) is a morphogen with important functions in embryonic organizing centers. It forms a gradient in the extracellular space by free diffusion, interaction with the extracellular matrix (ECM), and receptor-mediated endocytosis.

Sequential Vaccination Against Appears as Immunologically Safe in Clinically Stable Kidney Transplant Recipients.

Vaccination against is advised for transplant recipients to reduce morbidity and mortality associated with invasive pneumococcal disease. However, data on alloantibodies after sequential vaccination (with a pneumococcal conjugate vaccine followed by a polysaccharide vaccine) are still lacking. In the current study, we determined HLA class I and II and major histocompatibility class I-related chain A (MICA) antibodies in 41 clinically stable kidney transplant recipients.

A Surface-Active Pt(II) Bis-N-Heterocyclic Carbene (NHC) Complex for Interface-Enhanced Supported Ionic Liquid Phase (SILP) Catalysis.

We present the preparation and investigation of a fluorine-free surface-active bis-N-heterocyclic carbene (NHC) platinum(II) complex - trans-[Pt(mPEGCIm)Cl] - for interface-enhanced supported ionic liquid phase (SILP) catalysis within a group of (mPEG)-substituted ionic liquids (ILs) ([(mPEG)Im][A] ILs). The complex was characterized by means of single-crystal X-ray diffraction (scXRD) analysis and multinuclear (H, C, Pt) NMR spectroscopy, indicating the presence of two almost equimolar syn-anti-rotamers of the square-planar complex in solution. Angle-resolved X-ray photoelectron spectroscopy (ARXPS) revealed pronounced interface-accumulation of trans-[Pt(mPEGCIm)Cl] in IL solutions of [(mPEG)Im][A] (A=I and PF ).

HBV shows different levels of adaptation to HLA class I-associated selection pressure correlating with markers of replication.

Background & Aims: Immune responses by CD8 T cells are essential for control of HBV replication. Although selection of escape mutations in CD8 T-cell epitopes has been previously described in HBV infection, its overall influence on HBV sequence diversity and correlation with markers of HBV replication remain unclear.

Methods: Whole-genome sequencing was applied to HBV isolates from 532 patients with chronic HBV infection and high-resolution HLA class I genotyping.

Early CYP3A5 Genotype-Based Adjustment of Tacrolimus Dosage Reduces Risk of De Novo Donor-Specific HLA Antibodies and Rejection among CYP3A5-Expressing Renal Transplant Patients.

Background/objectives: Our previous retrospective single-center cohort study found, at 3-year follow-up, a trend toward low tacrolimus trough levels and an increased risk of de novo donor-specific anti-HLA antibodies (DSAs) and of antibody-mediated rejection (ABMR) in CYP3A5-expressing patients. Determining CYP3A5-expression status immediately after renal transplant would allow early genotype-based dosage adjustment of tacrolimus and might prevent the occurrence of de novo DSAs and ABMR, improving transplant outcome.

Methods: 160 renal allograft recipients who underwent renal transplant at the University Hospital Essen between May 2019 and May 2022 were genotyped for the rs776746 polymorphism within the first two weeks after transplant, and genotype-based dose adjustment of tacrolimus was performed for the follow-up of 2 years.

A bis-Phenolate Carbene-Supported bis-μ-Oxo Iron(IV/IV) Complex with a [Fe(μ-O)Fe] Diamond Core Derived from Dioxygen Activation.

The diiron(II) complex, [(OCO)Fe(MeCN)] (, MeCN = acetonitrile), supported by the bis-phenolate carbene pincer ligand, 1,3-bis(3,5-di--butyl-2-hydroxyphenyl)benzimidazolin-2-ylidene (OCO), was synthesized and characterized by single-crystal X-ray diffraction, H nuclear magnetic resonance, infrared (IR) vibrational, ultraviolet/visible/near-infrared (UV/vis/NIR) electronic absorption, Fe Mössbauer, X-band electron paramagnetic resonance (EPR) and SQUID magnetization measurements. Complex activates dioxygen to yield the diferric, μ-oxo-bridged complex [(OCO)Fe(py)(μ-O)Fe(O(C═O)O)(py)] () that was isolated and fully characterized. In , one of the iron-carbene bonds was oxidized to give a urea motif, resulting in an O(C═O)O binding site, while the other Fe(OCO) unit remained unchanged.

A Selective Iron(I) Hydrogenation Catalyst.

Iron is the most abundant transition metal of the Earth's crust, and the understanding of its function in key technologies, such as catalysis, is highly important. We report here on an iron(I) hydrogenation catalyst. Our catalyst activates hydrogen via heterolytic bond cleavage, forms a monohydride, and hydrogenates polar double bonds via a bimetallic pathway (potassium-assisted hydride transfer).

Cooperative spin crossover leading to bistable and multi-inert system states in an iron(III) complex.

Cooperativity among spin centres has long been the royal road in spin crossover (SCO) research to impose magnetic bistability in terms of thermal hysteresis. In this work we access magnetic multi-inert states of the iron(III) compound {FeL[B(Ph)]} ≡ FeB at low temperature, in addition to thermal bistability. The packing of the low-spin and high-spin forms of crystalline FeB differs only marginally what ultimately leads to structural conservatism.

Differential Abundance of DNA Damage Sensors and Innate Immune Signaling Proteins in Inositol Polyphosphate 4-Phosphatase Type II-Negative Triple-Negative Breast Cancer Classified by Immunotype.

The influence of neoplastic cells on the tumor microenvironment is poorly understood. In this study, eight patient samples representing two immunotypes of triple-negative breast cancer (TNBC), defined by quantitative histologic criteria as T-cell desert and T-cell infiltrated (TCI), were compared via label-free quantitative protein mass spectrometry of material extracted directly from targeted regions of formalin-fixed, paraffin-embedded tissue sections. Of 2934 proteins quantitated, 439 were significantly differentially abundant, among which 361 were overabundant in TCI-TNBC.

From d to d: Iron(0) and Iron(I) Complexes Complete the Series of Eight Fe Oxidation States within the TIMMN Ligand Framework.

Reduction of the ferrous precursor [(TIMMN)Fe(Cl)] () (TIMMN = ris-[(3-mesitylidazol-2-ylidene)ethyl]amie) to the low-valent iron(0) complex [(TIMMN)Fe(CO)] () is presented, where the tris(N-heterocyclic carbene) (NHC) ligand framework remains intact, yet the coordination mode changed from 3-fold to 2-fold coordination of the carbene arms. Further, the corresponding iron(I) complexes [(TIMMN)Fe(L)] (L = free site, η-N, CO, py) () are synthesized and fully characterized. Complexes - demonstrate the notable steric and electronic flexibility of the TIMMN ligand framework by variation of the Fe-N anchor and Fe-carbene distances and the variable size of the axial cavity occupation.

Risk Stratification Before Living Donor Kidney Transplantation in Patients With Preformed Donor-specific Antibodies by Different Crossmatch Methods.

Background: Preformed donor-specific HLA antibodies (DSA) are a well-known risk factor in kidney transplantation. There is still considerable debate, however, about the optimal risk stratification among patients with preformed DSA. Additionally, data on the prognostic value of different crossmatch assays in DSA-positive patients are scarce.

Dibenzoazepine hydrazine is a building block for -alkene hybrid ligands: exploratory syntheses of complexes of Cu, Fe, and Li.

The new hydrazine 5-dibenzo[,]azepin-5-amine (2) reacts with P- and Si-electrophiles deprotonation to afford P(III)-, P(V)-, and TMS-hydrazides 3-8 and with carbonyl electrophiles acid-free condensation to the -substituted hydrazones 9-12 that are potential -alkene ligands. While β-ketohydrazone 9 and α-dihydrazone 10 react with [Mes(Cu)], [Cu(NCCCH)]PF, and FeCl(THF) to afford complexes devoid of alkene interaction, [Cu(OTf)]·CH reacts with the α-keto hydrazone 11 or with , dimethyl-hydrazone 12 to form the neutral dimeric Cu(I) complex 18 with bridging Cu(I)-alkene interactions or the tetrahedral cationic complex 19 in which 12 binds as a bidentate hydrazone-alkene ligand, respectively. The surprising stability of the alkene coordination in complexes 18 and 19 prevents substitutions with, , PPh.

Influence of Donor-Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores.

In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates.

Monocyte-derived alveolar macrophages are key drivers of smoke-induced lung inflammation and tissue remodeling.

Smoking is a leading risk factor of chronic obstructive pulmonary disease (COPD), that is characterized by chronic lung inflammation, tissue remodeling and emphysema. Although inflammation is critical to COPD pathogenesis, the cellular and molecular basis underlying smoking-induced lung inflammation and pathology remains unclear. Using murine smoke models and single-cell RNA-sequencing, we show that smoking establishes a self-amplifying inflammatory loop characterized by an influx of molecularly heterogeneous neutrophil subsets and excessive recruitment of monocyte-derived alveolar macrophages (MoAM).

The synthesis and characterization of an iron(VII) nitrido complex.

Complexes of iron in high oxidation states are captivating research subjects due to their pivotal role as active intermediates in numerous catalytic processes. Structural and spectroscopic studies of well-defined model complexes often provide evidence of these intermediates. In addition to the fundamental molecular and electronic structure insights gained by these complexes, their reactivity also affects our understanding of catalytic reaction mechanisms for small molecule and bond-activation chemistry.

Recruiting refugees and migrants as potential hematopoietic stem cell donors to serve patients of comparable ethnicities with rare human leucocyte antigen patterns - The BluStar.NRW project in North Western Germany.

Currently, approximately 19 million people with a migration background live in Germany. The majority of those descend from regions where the population has a genetically different distribution of HLA antigens when compared to the HLA frequencies usually found in North Western Europe. In case of severe haematological disorders of these individuals, allogeneic stem cell transplantation may be the treatment of choice.

Learning image representations for anomaly detection: Application to discovery of histological alterations in drug development.

We present a system for anomaly detection in histopathological images. In histology, normal samples are usually abundant, whereas anomalous (pathological) cases are scarce or not available. Under such settings, one-class classifiers trained on healthy data can detect out-of-distribution anomalous samples.

Evolution of a 'privileged' P-alkene ligand: added planar chirality beats BINOL axial chirality in catalytic asymmetric C-C bond formation.

Alkene planar chirality is introduced in the 'privileged' P-alkene phosphoramidite ligand 1. The resulting diastereomeric ligands (p)-5 and (p)-5 form optically pure complexes of Rh(I) and Pd(II), which catalyze conjugate additions of boron C-nucleophiles to enones and allylic alkylations, respectively. In the Rh-catalyzed reaction, the planar chirality of the alkene exerts absolute enantiocontrol over the potent BINOL auxiliary.

Self-Assembled Supported Ionic Liquids.

Separation and reuse of the catalytically active metal complexes are persistent issues in homogeneous catalysis. Supported Ionic Liquid Phase (SILP) catalysts, where the catalytic center is dissolved in a thin film of a stable ionic liquid, deposited on a solid support, present a promising alternative. However, the dissolution of the metal center in the film leaves little control over its position and its activity.

Stereochemical Stability of Planar-Chiral Benzazepine Tricyclics: Inversion Energies of P- and S-Alkene Ligands.

Inversion barriers Δ for planar chiral phosphine-alkene and sulfonamide-alkene hybrid ligands based on phenyl-dibenz[]azepine have been determined by density-functional theory calculations. Analysis of the structural and electronic characteristics of the minima and transition states explains the magnitudes of Δ and the geometrical changes during the inversion process. The steric repulsion caused by bulky substituents attached to the azepine nitrogen atom has a pronounced effect on the Δ value, explaining, inter alia, the stereochemical stability of the P- and S-alkene ligands when compared to the fluxional parent compound where X = H.

App-Controlled Treatment Monitoring and Support for Patients With Head and Neck Cancer Undergoing Radiotherapy: Results From a Prospective Randomized Controlled Trial.

Background: Head and neck cancers (HNCs) are very common malignancies, and treatment often requires multimodal approaches, including radiotherapy and chemotherapy. Patients with HNC often display a high symptom burden, both due to the disease itself and the adverse effects of the multimodal therapy. Close telemonitoring of symptoms and quality of life during the course of treatment may help to identify those patients requiring early medical support.

Swift C-C bond insertion by a 12-electron palladium(0) surrogate.

The selective activation of C-C bonds holds vast promise for catalysis. So far, research has been primarily directed at rhodium and nickel under harsh reaction conditions. Herein, we report C-C insertion reactions of a 12-electron palladium(0) surrogate stabilized by a cyclic(alkyl)(amino) carbene (CAAC) ligand.

Closed Synthetic Cycle for Nickel-Based Dihydrogen Formation.

Dihydrogen evolution was observed in a two-step protonation reaction starting from a Ni precursor with a tripodal N-heterocyclic carbene (NHC) ligand. Upon the first protonation, a Ni monohydride complex was formed, which was isolated and fully characterized. Subsequent protonation yields H via a transient intermediate (INT) and an isolable Ni acetonitrile complex.