Chemocatalytic Conversion of Dinitrogen to Ammonia Mediated by a Tungsten Complex.

Whereas molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase, corresponding tungsten complexes were in most cases found to be catalytically inactive. Herein, we present a modified pentadentate tetrapodal (pentaPod) phosphine ligand in which two dimethylphosphine groups of the pentaPodMe (P5Me) ligand have been replaced with phospholanes (Pln). The derived molybdenum complex [Mo(N2)P5Pln] generates 22 and the analogous tungsten complex [W(N2)P5Pln] 7 equivalents of NH3 from N2 in the presence of 180 equiv.

Affectivity as stance: multimodal stance-taking in audiovisual documentations of Polish and German parliamentary debates.

This paper presents a media-aesthetic framework to study affectivity as a stance. This framework opens up a new perspective on multimodal affective stance-taking in the context of specific media ecologies. It exemplifies this new approach with case studies of the official audiovisual documentation of political debates in the German Bundestag and the Polish Sejm.

Renal resistive index assessment by intraoperative transesophageal echocardiography is associated with acute kidney injury after cardiac surgery: a prospective observational study.

Background: Acute kidney injury (AKI) is a major health burden after cardiac surgery. Renal vasoconstriction and venous congestion can be assessed via transesophageal echocardiography (TEE). The primary objective is to determine feasibility of measuring intraoperative Renal resistive index (RRI) and portal vein pulsatility fraction (PF) by TEE.

Decoding Insulin Secretory Granule Maturation Using Genetically Encoded pH Sensors.

Insulin is a peptide hormone secreted from pancreatic beta cells to regulate blood glucose homeostasis. Maturation of active insulin occurs within insulin secretory granules (ISG) by acidification of the lumen and enzymatic cleavage of insulin before secretion. This process is dysregulated in diabetes, and many questions remain on how the cell controls insulin maturation.

Disparities in Demographics in Hip Arthroplasty Between U.S. Active Duty Military and the ACS-NSQIP Clinical Registry.

Introduction: Patient demographics, such as sex and age, are known risk factors for undergoing revision following primary total hip arthroplasty (THA). The military population is unique because of the increased rates of primary and secondary osteoarthritis of the hip. Treatment options are limited for returning patients to their line of duty; however, THA has been shown to be an effective option.

Comparison of Retinal Metabolic Activity and Structural Development between rd10 Mice and Normal Mice Using Multiphoton Fluorescence Lifetime Imaging Microscopy.

Fluorescence lifetime imaging microscopy (FLIM) is a technique that analyzes the metabolic state of tissues based on the spatial distribution of fluorescence lifetimes of certain interacting molecules. We used multiphoton FLIM to study the metabolic state of developing C57BL6/J and rd10 retinas based on the fluorescence lifetimes of free versus bound nicotinamide adenine dinucleotide and nicotinamide adenine dinucleotide phosphate (NAD(P)H), with free NAD(P)H percentages suggesting increased glycolysis and bound NAD(P)H percentages indicating oxidative phosphorylation. The mice were sacrificed and enucleated at various time points throughout their first 3 months of life.

Scaling up polarized RPE cell supernatant production on parylene membrane.

Age-related macular degeneration (AMD), a leading cause of vision loss, primarily arises from the degeneration of retinal pigment epithelium (RPE) and photoreceptors. Current therapeutic options for dry AMD are limited. Encouragingly, cultured RPE cells on parylene-based biomimetic Bruch's membrane demonstrate characteristics akin to the native RPE layer.

A Lack of Generalizability-Total Knee Demographics in the Active Duty Population.

Introduction: Age and sex are known demographic risk factors for requiring revision surgery following primary total knee arthroplasty (TKA). Military service members are a unique population with barriers to long-term follow up after surgery. This study aims to compare demographic data between active duty military personnel and a nationwide sample to identify differences that may impact clinical and economic outcomes.

Suppression of sweetness: evidence for central mechanism for suppression of sweetness from sucrose by citric acid.

The underlying mechanisms of taste interactions in humans are not well understood, and three mechanisms have been proposed, namely a chemical interaction, a peripheral physiological, and a central mechanism. In the present study, it was investigated which of these mechanisms causes the suppression of sweetness by citric acid. This was investigated using a split-tongue gustometer that can stimulate the two sides of the tongue with different stimuli simultaneously, enabling a comparison of sucrose and citric acid presented either separately on each side of the tongue simultaneously or in a mixture on one side.

Oral opioid prescribing to active duty US military personnel: a cross-sectional population.

Introduction: While civilian opioid prescriptions have seen a dramatic decline in recent years, there are few studies investigating trends in opioid prescription in the active duty military population. We evaluated oral opioid prescribing patterns to active duty military personnel in the Military Health System (MHS) from 2017 to 2020 to determine the incidence of opioid prescriptions as well as demographic and military-specific risk factors for receiving an oral opioid prescription.

Methods: The MHS Data Repository was queried from 2017 to 2020 to identify all outpatient oral opioid prescriptions to active duty military personnel in August of each year as well as demographic information on the study population.

Development of Highly Fluorogenic Styrene Probes for Visualizing RNA in Live Cells.

Styrene dyes are useful imaging probes and fluorescent sensors due to their strong fluorogenic responses to environmental changes or binding macromolecules. Previously, indole-containing styrene dyes have been reported to selectively bind RNA in the nucleolus and cytoplasm. However, the application of these indole-based dyes in cell imaging is limited by their moderate fluorescence enhancement and quantum yields, as well as relatively high background associated with these green-emitting dyes.

Development of a Bispecific Antibody Targeting Clinical Isolates of Acinetobacter baumannii.

Background: We previously reported developing 2 anticapsular monoclonal antibodies (mAbs) as a novel therapy for Acinetobacter baumannii infections. We sought to determine whether a bispecific mAb (bsAb) could improve avidity and efficacy while maximizing strain coverage in one molecule.

Methods: Humanized mAb 65 was cloned into a single-chain variable fragment and attached to humanized mAb C8, combining their paratopes into a single bsAb (C73).

N Reduction versus H Evolution in a Molybdenum- or Tungsten-Based Small-Molecule Model System of Nitrogenase.

Molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase. In comparison, analogous tungsten complexes have in most cases found to be catalytically inactive. Herein, a tungsten complex was shown to be supported by a pentadentate tetrapodal (pentaPod) phosphine ligand, under conditions of N fixation, primarily catalyzes the hydrogen evolution reaction (HER), in contrast to its Mo analogue, which catalytically mediates the nitrogen-reduction reaction (N RR).

Insights into Metabolic Activity and Structure of the Retina through Multiphoton Fluorescence Lifetime Imaging Microscopy in Mice.

Fluorescence lifetime imaging microscopy (FLIM) evaluates the metabolic state of tissue based on reduced nicotinamide adenine dinucleotide (NAD(P)H) and flavin adenine dinucleotide (FAD). Fluorescence lifetime imaging ophthalmoscopy (FLIO) can image the fundus of the eyes, but cannot detect NAD(P)H. We used multiphoton FLIM to study the metabolic state of the retina in fixed eyes of wild-type mice C57BL6/J.

Bladder cancer cells shift rapidly and spontaneously to cisplatin-resistant oxidative phosphorylation that is trackable in real time.

Genetic mutations have long been recognized as drivers of cancer drug resistance, but recent work has defined additional non-genetic mechanisms of plasticity, wherein cancer cells assume a drug resistant phenotype marked by altered epigenetic and transcriptional states. Currently, little is known about the real-time, dynamic nature of this phenotypic shift. Using a bladder cancer model of nongenetic plasticity, we discovered that rapid transition to drug resistance entails upregulation of mitochondrial gene expression and a corresponding metabolic shift towards the tricarboxylic acid cycle and oxidative phosphorylation.

Tungsten and molybdenum dinitrogen complexes supported by a pentadentate tetrapodal phosphine ligand: comparative spectroscopic, electrochemical and reactivity studies.

The tungsten dinitrogen complex [W(N)(PPP)] (2) (PPP = [2-({bis[3-(diphenylphosphino)propyl]-phosphino}methyl)-2-methylpropane-1,3-diyl]bis(dimethylphosphine)) is synthesized and characterized by X-ray diffraction as well as IR and NMR spectroscopies, showing strong analogies to its molybdenum analogue [Mo(N)(PPP)] (1). Whereas cyclic voltammetry studies indicate very similar redox potentials, detailed electrochemical and IR-spectroelectrochemical investigations reveal characteristic differences between 1 and 2 upon electrochemical oxidation in THF. Protonation of 2 with HBAr (BAr = tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) leads to the hydrazido(2-) derivative 3 which is spectroscopically characterized as well.

SARS-CoV2 infects pancreatic beta cells in vivo and induces cellular and subcellular disruptions that reflect beta cell dysfunction.

Increasing evidence of new-onset diabetes during the COVID19 pandemic indicates that the SARS-CoV2 virus may drive beta-cell dysfunction leading to diabetes, but it is unclear if it is a primary or secondary effect. Here, we present evidence of SARS-CoV-2 infection of pancreatic beta cells using a robust and reproducible non-human primates model of mild to moderate COVID19 pathogenesis. Pancreas from SARS-CoV-2 infected subjects were positive for the SARS-CoV2 spike protein by immunohistochemistry and structures indicative of viral replication were evident by electron microscopy.

Complex wavelet filter improves FLIM phasors for photon starved imaging experiments.

Fluorescence lifetime imaging microscopy (FLIM) with phasor analysis provides easy visualization and analysis of fluorophores' lifetimes which is valuable for multiple applications including metabolic imaging, STED imaging, FRET imaging and functional imaging. However, FLIM imaging typically suffers from low photon budgets, leading to unfavorable signal to noise ratios which in many cases prevent extraction of information from the data. Traditionally, median filters are applied in phasor analysis to tackle this problem.

Hypertonic Dextrose Stimulates Chondrogenic Cells to Deposit Collagen and Proliferate.

Objective: Hypertonic dextrose (HD) injections (prolotherapy) for osteoarthritis are reported to reduce pain. Cartilage regeneration is hypothesized as a mechanism. This study identifies an HD concentration that stimulates chondrogenic cells to increase metabolic activity and assesses whether this concentration affects collagen deposition and proliferation.

Live-cell imaging of glucose-induced metabolic coupling of β and α cell metabolism in health and type 2 diabetes.

Type 2 diabetes is characterized by β and α cell dysfunction. We used phasor-FLIM (Fluorescence Lifetime Imaging Microscopy) to monitor oxidative phosphorylation and glycolysis in living islet cells before and after glucose stimulation. In healthy cells, glucose enhanced oxidative phosphorylation in β cells and suppressed oxidative phosphorylation in α cells.

Intralacrimal Sustained Delivery of Rapamycin Shows Therapeutic Effects without Systemic Toxicity in a Mouse Model of Autoimmune Dacryoadenitis Characteristic of Sjögren's Syndrome.

Sjögren's syndrome (SS) is an autoimmune disease associated with severe exocrinopathy, which is characterized by profound lymphocytic infiltration (dacryoadenitis) and loss of function of the tear-producing lacrimal glands (LGs). Systemic administration of Rapamycin (Rapa) significantly reduces LG inflammation in the male Nonobese Diabetic (NOD) model of SS-associated autoimmune dacryoadenitis. However, the systemic toxicity of this potent immunosuppressant limits its application.

A Chatt-Type Catalyst with One Coordination Site for Dinitrogen Reduction to Ammonia.

Invited for the cover of this issue is the group of Felix Tuczek at Christian-Albrechts-Universität zu Kiel. The image depicts the coordination geometry of the catalyst reported in this work. Read the full text of the article at 10.

Taste Interactions between Sweetness of Sucrose and Sourness of Citric and Tartaric Acid among Chinese and Danish Consumers.

Tastes interact in almost every consumed food or beverage, yet many aspects of interactions, such as sweet-sour interactions, are not well understood. This study investigated the interaction between sweetness from sucrose and sourness from citric and tartaric acid, respectively. A cross-cultural consumer study was conducted in China ( = 120) and Denmark ( = 139), respectively.

A Chatt-Type Catalyst with One Coordination Site for Dinitrogen Reduction to Ammonia.

With [Mo(N )(P PP )] the first Chatt-type complex with one coordination site catalytically converting N to ammonia is presented. Employing SmI as reductant and H O as proton source 26 equivalents of ammonia are generated. Analogous Mo -N complexes supported by a combination of bi- and tridentate phosphine ligands are catalytically inactive under the same conditions.

A porous and redox active ferrocenedicarboxylic acid based aluminium MOF with a MIL-53 architecture.

A metallocene based linker 1,1'-ferrocenedicarboxylic acid (H2FcDC) was used to synthesise the first permanently porous ferrocenedicarboxylate, exhibiting a MIL-53 architecture. This compound Al-MIL-53-FcDC [Al(OH)(FcDC)] is obtained in glass vials under mild synthesis conditions at ≤100 °C and after a short reaction time of 90 min. The crystal structure was determined from powder X-ray diffraction data and the compound shows porosity towards N2 and H2O, exhibiting a BET surface area of 340 m2 g-1.