From a P-Bridging Phosphaketene to μ-Phosphinidenide and μ-Diphosphaurea Units at a Dinickel Core.

Salt metathesis of dinickel(II) complex LNiBr (1; L is a dinucleating pyrazolate ligand with two β-diketiminato chelate arms) with Na(OCP) ⋅ (dioxane) yielded LNi(PCO) (2) with a P-bridging phosphaethynolate. Further reaction of 2 with benzyl isocyanide or with an N-heterocyclic carbene (NHC) triggered decarbonylation and gave LNi(PCN-CHPh) (3) and LNiP(NHC) (4) with P-bridging cyanophosphide and NHC-phosphinidenide, respectively. Electronic structure analysis indicated a μ-η : η binding mode of the PCO anion between the two Ni ions in 2, which is even more pronounced for the [PCN(-CHPh)] anion in 3.

Associations between Psychosocial Working Conditions and Work-Specific Self-Efficacy Beliefs Among Employees Receiving Psychotherapeutic Consultation at Work.

Purpose: By considering work-related aspects during early intervention and treatment of employees with (subclinical) symptoms of common mental disorders, psychotherapeutic consultation at work (PT-W) aims to increase work-specific self-efficacy (SE) to finally reduce sickness absence and contribute to successful return to work. This study, thus, aims to investigate interrelations between working conditions and work-specific SE among employees before receiving PT-W.

Methods: The study uses baseline data of a randomized controlled trial testing the efficacy of PT-W in Germany (n = 535).

Cleavage of Carbodicarbenes with NO for Accessing Stable Diazoalkenes: Two-Fold Ligand Exchange at a C(0)-Atom.

The cleavage of carbophosphinocarbenes and carbodicarbenes with nitrous oxide (NO) leads to the formation of room-temperature stable diazoalkenes. The utility of PhP/N and NHC/N ligand exchange reactions were demonstrated by accessing novel benzimidazole- and benzothiazole derived diazoalkenes, which are not accessible by the current state-of-the-art methods. The stable diazoalkenes subsequently allow further ligand exchange reactions at C(0) with carbon monoxide, isocyanide, or a diamidocarbene (DAC).

PhPCN: A stable reagent for carbon-atom transfer.

Precise modification of a chemical site in a molecule at the single-atom level is one of the most elegant yet difficult transformations in chemistry. A reagent specifically designed for chemoselective introduction of monoatomic carbon is a particularly formidable challenge. Here, we report a straightforward, azide-free synthesis of a crystalline and isolable diazophosphorus ylide, PhPCN, a stable compound with a carbon atom bonded to two chemically labile groups, triphenylphosphine (PPh) and dinitrogen (N).

Cycloadditions of Diazoalkenes with P and tBuCP: Access to Diazaphospholes.

Diazoalkenes readily react with tert-butylphosphaalkyne (tBuCP) and white phosphorus (P) to afford novel phosphorus heterocycles, 3H-1,2,4-diazamonophospholes and 1,2,3,4-diazadiphospholes. Both species represent rare examples of neutral heterophospholes. The mechanism of formation and the electronic structures of these formal (3+2) cycloaddition products were analyzed computationally.

[Psychotherapeutic consultation at work: associations between company size and psychosomatic health].

Background: The utilization of psychotherapeutic consultation at work (PT-A) has so far been investigated in large enterprises (LEs). These differ structurally from small(est) and medium-sized enterprises (SMEs). Differences in the user profiles of a PT‑A with regard to psychosomatic health, work-related self-efficacy, and work ability depending on company size have hardly been investigated.

[Implementation of psychotherapeutic consultation at work (PT-A): expectations, announcement, and use : Results of the friaa-study].

Introduction: Psychotherapeutic consultation at work (PT-A) offers easily accessible, short-term support for employees experiencing psychological stress. The aim of the study was to evaluate aspects of the implementation regarding announcement, access, and use of the PT‑A.

Methods: The study was conducted as part of a randomized controlled trial (RCT) called "Early Intervention in the Workplace".

para-Aminoazobenzenes-Bipolar Redox-Active Molecules.

Azobenzenes (ABs) are versatile compounds featured in numerous applications for energy storage systems, such as solar thermal storages or phase change materials. Additionally, the reversible one-electron reduction of these diazenes to the nitrogen-based radical anion has been used in battery applications. Although the oxidation of ABs is normally irreversible, 4,4'-diamino substitution allows a reversible 2e oxidation, which is attributed to the formation of a stable bis-quinoidal structure.

[Mental health problems among employees: service use and costs to the German healthcare system].

Background: Service use among employees with mental health problems and the associated costs for the health and social system have not yet been systematically analysed in studies or have only been recorded indirectly. The aim of this article is to report the service use in this target group, to estimate the costs for the health and social system and to identify possible influencing factors on the cost variance.

Methods: As part of a multicentre study, use and costs of health and social services were examined for a sample of 550 employees with mental health problems.

Checkpoint inhibition enhances cell contacts between CD4 T cells and Hodgkin-Reed-Sternberg cells of classic Hodgkin lymphoma.

Although checkpoint molecules like CTLA-4 and PD1 have been described several years ago, checkpoint inhibitors such as nivolumab (an anti-PD-1 antibody) have only recently been used to treat classic Hodgkin lymphoma (cHL). Several studies have shown convincing therapeutic effects of nivolumab in cHL. However, the mechanism of action of nivolumab in cHL is not fully understood.

Mesoionic N-Heterocyclic Olefins as Initiators for the Lewis Pair Polymerization of Epoxides.

Mesoionic N-heterocyclic olefins (mNHOs) have recently emerged as a novel class of highly nucleophilic and super-basic σ-donor compounds. Making use of these properties in synthetic polymer chemistry, it is shown that a combination of a specific mNHO and a Mg-based Lewis acid (magnesium bis(hexamethyldisilazide), Mg(HMDS)) delivers poly(propylene oxide) in quantitative yields from the polymerization of the corresponding epoxide (0.1 mol% mNHO loading).

Dicationic Acridinium/Carbene Hybrids as Strongly Oxidizing Photocatalysts.

A new design concept for organic, strongly oxidizing photocatalysts is described based upon dicationic acridinium/carbene hybrids. A highly modular synthesis of such hybrids is presented, and the dications are utilized as novel, tailor-made photoredox catalysts in the direct oxidative C-N coupling. Under optimized conditions, benzene and even electron-deficient arenes can be oxidized and coupled with a range of -heterocycles in high to excellent yields with a single low-energy photon per catalytic turnover, while commonly used acridinium photocatalysts are not able to perform the challenging oxidation step.

Pyridinium-Derived Mesoionic N-Heterocyclic Olefins (py-mNHOs).

Mesoionic polarization allows access to electron-rich olefins that have found application as organocatalysts, ligands, or nucleophiles. Herein, we report the synthesis and characterization of a series of 3-methylpyridinium-derived mesoionic olefins (py-mNHOs). We used a DFT-supported design concept, which showed that the introduction of aryl groups in the 1-, 2-, 4-, and 6-positions of the heterocyclic core allowed the kinetic stabilization of the novel mesoionic compounds.

[3D/4D strategic lymph node diagnostics : The 4D representation of the human lymph node enables the observation and interpretation of the immune system in space and time].

Background: Lymph-node diagnostics is performed using thin sections, with help of immunohistochemistry by light microscopy and supplemented by molecular pathology.

Objectives: Which are the scientific and diagnostic perspectives of 3D and 4D lymph node investigations, using laser, scanning, and computer technologies? What is the impact of machine learning in complex data analysis.

Results: It was shown in different investigations that the analysis in space and time (3D/4D) of lymph node tissue is able to provide a lot of new information concerning biology and diagnostics and enable excellent evaluations applying machine learning.

Transcriptional reprogramming by mutated IRF4 in lymphoma.

Disease-causing mutations in genes encoding transcription factors (TFs) can affect TF interactions with their cognate DNA-binding motifs. Whether and how TF mutations impact upon the binding to TF composite elements (CE) and the interaction with other TFs is unclear. Here, we report a distinct mechanism of TF alteration in human lymphomas with perturbed B cell identity, in particular classic Hodgkin lymphoma.

From Squaric Acid Amides (SQAs) to Quinoxaline-Based SQAs─Evolution of a Redox-Active Cathode Material for Organic Polymer Batteries.

The search for new redox-active organic materials (ROMs) is essential for the development of sustainable energy-storage solutions. In this study, we present a new class of cyclobuta[]quinoxaline-1,2-diones or squaric acid quinoxalines (SQXs) as highly promising candidates for ROMs featuring exceptional stability and high redox potentials. While simple 1,2- and 1,3-squaric acid amides (SQAs), initially reported by Hünig and coworkers decades ago, turned out to exhibit low stability in their radical cation oxidation states, we demonstrate that embedding the nitrogen atoms into a quinoxaline heterocycle leads to robust two-electron SQX redox systems.

Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111).

Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes.

Clonal composition and differentiation stage of human CD30 B cells in reactive lymph nodes.

Introduction: Normal CD30 B cells represent a distinct B-cell differentiation stage with features of strong activation. We lack an in depth understanding of these cells, because they are not present in peripheral blood and are typically very rare in reactive lymphoid organs. CD30 B cells have been discussed as a potential precursor population for the malignant CD30 Hodgkin and Reed-Sternberg cells in classical Hodgkin lymphoma.

Pushing the Upper Limit of Nucleophilicity Scales by Mesoionic N-Heterocyclic Olefins.

A series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO Et) , which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k (20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and s parameters of the mNHOs according to the correlation lg k (20 °C)=s (N+E).

Three-dimensional human germinal centers of different sizes in patients diagnosed with lymphadenitis show comparative constant relative volumes of B cells, T cells, follicular dendritic cells, and macrophages.

Germinal centers (GCs) are some of the most important structures in the human immune system. As such, their cell types and functions have been thoroughly investigated. B cells, T cells, follicular dendritic cells (FDCs), and macrophages have widely been found to typically be aggregated in GCs.