Unravelling the Role of Sterically Encumbered Ligands in Tuning the Magnetic Properties of Lanthanide-Based D Single-Ion Magnets.

Isostructural Dy(III) and Er(III) complexes [L Ln(HO)][I] ⋅ L  ⋅ (CHCl) (Ln=Dy (1), Er (3)) and [L Ln(HO)][I] ⋅ L  ⋅ (CHCl) (Ln=Dy (2), Er (4)), with distorted pentagonal bipyramidal geometry (D) around the central metal were synthesized by utilizing two bulky phosphonamide ligands, adamantyl phosphonamide, (Ad)P(O)(NHPr) (L) and carbazolyl phosphoramide (Cz)P(O)(NHPr) (L). The resultant complexes were investigated for their magnetic properties in order to elucidate the impact of modification of the coordinating P-O bond environment either by increasing steric bulk and/or introduction of a third P-N bond at the central phosphorus atom. Magnetic studies revealed substantial energy barriers (U) of 640 K and 491 K for Dy compounds 1 and 2, respectively, rendering them as some of the best-performing air-stable SIMs amongst the class of SIMs with D symmetry.

Millets for a sustainable future.

Our current agricultural system faces a perfect storm-climate change, burgeoning population, and unpredictable outbreaks like COVID-19 disrupt food production, particularly for vulnerable populations in developing countries. A paradigm shift in agriculture practices is needed to tackle these issues. One solution is the diversification of crop production.

Involvement of E3 Ubiquitin Ligases in Viral Infections of the Human Host.

Viral infections are one of the principal causes of global primary health crises, with increased rate of infection and mortality demonstrated by the newer progeny of viruses. Viral invasion of the host involves utilization of various cellular machinery. Ubiquitination is one of a few central regulatory systems used by viruses for establishment of the infections in the host.

Natural variation in the chickpea metabolome under drought stress.

Chickpea is the world's fourth largest grown legume crop, which significantly contributes to food security by providing calories and dietary protein globally. However, the increased frequency of drought stress has significantly reduced chickpea production in recent years. Here, we have performed a field experiment with 36 diverse chickpea genotypes to evaluate grain yield, photosynthetic activities and molecular traits related to drought stress.

Closed-Loop Therapy and Sleep in Young People Newly Diagnosed With T1D and Their Parents.

Background: A diagnosis of type 1 diabetes in a young person can create vulnerability for sleep. Historically it has been rare for young people to be offered a closed-loop system soon after diagnosis meaning that studies examining sleep under these circumstances in comparison with standard treatment have not been possible. In this study, we examine sleep in young people (and their parents) who were provided with hybrid closed-loop therapy at diagnosis of type 1 diabetes versus those who receive standard treatment over a 2-year period.

Accelerating wheat improvement through trait characterization: advances and perspectives.

Wheat (Triticum spp.) is a primary dietary staple food for humanity. Many wheat genetic resources with variable genomes have a record of domestication history and are widespread throughout the world.

The Potential Clinical Utility of an Artificial Intelligence Model for Identification of Vertebral Compression Fractures in Chest Radiographs.

Purpose: To assess the ability of the Annalise Enterprise CXR Triage Trauma (Annalise AI Pty Ltd, Sydney, NSW, Australia) artificial intelligence model to identify vertebral compression fractures on chest radiographs and its potential to address undiagnosed osteoporosis and its treatment.

Materials And Methods: This retrospective study used a consecutive cohort of 596 chest radiographs from four US hospitals between 2015 and 2021. Each radiograph included both frontal (anteroposterior or posteroanterior) and lateral projections.

Facile room-temperature synthesis of layered transition metal phosphonates hitherto unknown alkali metal -butyl phosphonates.

A facile room-temperature synthetic method is presented to produce alkali metal salts of -butyl phosphonic acid. The reaction between equimolar amounts of alkali metal carbonates and -butyl phosphonic acid in methanol results in the formation of [(BuPOH)Li(HO)·(HO)] (1), [(BuPO)Na(HO)] (2), and [(BuPOH)K(HO)] (3). Solid-state structures of these compounds have been confirmed by single-crystal X-ray diffraction studies and further validated using numerous spectroscopic and analytical techniques.

Intermediates involved in the reduction of SO: insight into the mechanism of sulfite reductases.

Sulfite reductases (SiRs) catalyze the reduction of SO to HS in biosynthetic sulfur assimilation and dissimilation of sulfate. The mechanism of the 6e/6H reduction of SO at the siroheme cofactor is debated, and proposed intermediates involved in this 6e reduction are yet to be spectroscopically characterized. The reaction of SO with a ferrous iron porphyrin is investigated, and two intermediates are trapped and characterized: an initial Fe(III)-SO species, which undergoes proton-assisted S-O bond cleavage to form an Fe(III)-SO species.

Effect of 48 Months of Closed-Loop Insulin Delivery on Residual C-Peptide Secretion and Glycemic Control in Newly Diagnosed Youth With Type 1 Diabetes: A Randomized Trial.

Objective: We evaluated the effect of long-term intensive metabolic control with hybrid closed-loop (CL) on residual C-peptide secretion and glucose control compared with standard insulin therapy in youth with type 1 diabetes over 48 months.

Research Design And Methods: Following the 24-month primary phase of a multicenter, randomized, parallel trial of 96 newly diagnosed youth aged 10 to 16.9 years, participants were invited to an extension phase using treatment allocated at randomization.

Comparative analysis of geotypic variations in the proteome of .

Cyanobacterium is a filamentous terrestrial prokaryotic organism widely distributed, which suggest its high adaptive potential to environmental or abiotic stress. Physiological parameters and proteomic analysis were performed in two accession of with the aim to elucidate the differences of physiological trails between distant geotypes, namely Antarctic (AN) and central European (CE). The result obtained clearly showed that the AN geotype demonstrates elevated levels of total phenols, flavonoids, carotenoids, and phycobiliproteins, indicative of its adaptation to environmental stress as referred by comparison to CE sample.

Evaluation of an Artificial Intelligence Model for Identification of Mass Effect and Vasogenic Edema on CT of the Head.

Background And Purpose: Mass effect and vasogenic edema are critical findings on CT of the head. This study compared the accuracy of an artificial intelligence model (Annalise Enterprise CTB) with consensus neuroradiologists' interpretations in detecting mass effect and vasogenic edema.

Materials And Methods: A retrospective stand-alone performance assessment was conducted on data sets of noncontrast CT head cases acquired between 2016 and 2022 for each finding.

Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde.

Electrocatalytic alcohol oxidation in acid offers a promising alternative to the kinetically sluggish water oxidation reaction toward low-energy H generation. However, electrocatalysts driving active and selective acidic alcohol electrochemical transformation are still scarce. In this work, we demonstrate efficient alcohol-to-aldehyde conversion achieved by reticular chemistry-based modification of the catalyst's immediate environment.

Long-term assessment of the NHS hybrid closed-loop real-world study on glycaemic outcomes, time-in-range, and quality of life in children and young people with type 1 diabetes.

Hybrid closed-loop (HCL) systems seamlessly interface continuous glucose monitoring (CGM) with insulin pumps, employing specialised algorithms and user-initiated automated insulin delivery. This study aimed to assess the efficacy of HCLs at 12 months post-initiation on glycated haemoglobin (HbA1c), time-in-range (TIR), hypoglycaemia frequency, and quality of life measures among children and young people (CYP) with type 1 diabetes mellitus (T1DM) and their caregivers in a real-world setting. Conducted between August 1, 2021, and December 10, 2022, the prospective recruitment took place in eight paediatric diabetes centres across England under the National Health Service England's (NHSE) HCL pilot real-world study.

Local CO reservoir layer promotes rapid and selective electrochemical CO reduction.

Electrochemical CO reduction reaction in aqueous electrolytes is a promising route to produce added-value chemicals and decrease carbon emissions. However, even in Gas-Diffusion Electrode devices, low aqueous CO solubility limits catalysis rate and selectivity. Here, we demonstrate that when assembled over a heterogeneous electrocatalyst, a film of nitrile-modified Metal-Organic Framework (MOF) acts as a remarkable CO-solvation layer that increases its local concentration by ~27-fold compared to bulk electrolyte, reaching 0.

Enhancement of the Rate of Surface Reactions by the Elastocapillary Effect.

We examined the effect of deformability of a solid substrate on the kinetics of a surface reaction that occurs between chemical species present in it and a liquid dispensed on it. In particular, we have dispensed aqueous solutions of gold and silver salt as sessile drops or as a liquid pool on a cross-linked film of poly(dimethylsiloxane) (PDMS). The PDMS surface contains organosilane (SiH), which reduces the salt, producing metallic nanoparticles at the solid-liquid interface.

Cost-Effectiveness of Closed-Loop Automated Insulin Delivery Using the Cambridge Hybrid Algorithm in Children and Adolescents with Type 1 Diabetes: Results from a Multicenter 6-Month Randomized Trial.

Background/objective: The main objective of this study is to evaluate the incremental cost-effectiveness (ICER) of the Cambridge hybrid closed-loop automated insulin delivery (AID) algorithm versus usual care for children and adolescents with type 1 diabetes (T1D).

Methods: This multicenter, binational, parallel-controlled trial randomized 133 insulin pump using participants aged 6 to 18 years to either AID (n = 65) or usual care (n = 68) for 6 months. Both within-trial and lifetime cost-effectiveness were analyzed.

Diabetic Ketoacidosis at Onset of Type 1 Diabetes and Glycemic Outcomes with Closed-Loop Insulin Delivery.

The presence of diabetic ketoacidosis (DKA) at diagnosis of type 1 diabetes (T1D) is associated with higher glycated hemoglobin levels over time. We evaluated whether hybrid-closed loop (HCL) therapy from onset of T1D could prevent the adverse impact of DKA at diagnosis on long-term glycemic outcomes. This was a posthoc analysis from 51 adolescents using HCL from diagnosis of T1D as part of the CLOuD trial (NCT02871089).

Low dose ribosomal DNA P-loop mutation affects development and enforces autophagy in Arabidopsis.

Arabidopsis contains hundreds of ribosomal DNA copies organized within the nucleolar organizing regions (NORs) in chromosomes 2 and 4. There are four major types of variants of rDNA, VAR1-4, based on the polymorphisms of 3' external transcribed sequences. The variants are known to be differentially expressed during plant development.

Cell-type proteomic and metabolomic resolution of early and late grain filling stages of wheat endosperm.

The nutritional value of wheat grains, particularly their protein and metabolite composition, is a result of the grain-filling process, especially in the endosperm. Here, we employ laser microdissection (LMD) combined with shotgun proteomics and metabolomics to generate a cell type-specific proteome and metabolome inventory of developing wheat endosperm at the early (15 DAA) and late (26 DAA) grain-filling stages. We identified 1803 proteins and 41 metabolites from four different cell types (aleurone (AL), sub-aleurone (SA), starchy endosperm (SE) and endosperm transfer cells (ETCs).

Reducing the vicissitudes of heterologous prochiral substrate catalysis by alcohol dehydrogenases through machine learning algorithms.

Alcohol dehydrogenases (ADHs) are popular catalysts for synthesizing chiral synthons a vital step for active pharmaceutical intermediate (API) production. They are grouped into three superfamilies namely, medium-chain (MDRs), short-chain dehydrogenase/reductases (SDRs), and iron-containing alcohol dehydrogenases. The former two are used extensively for producing various chiral synthons.

Quantifying the impact of dynamic plant-environment interactions on metabolic regulation.

A plant's genome encodes enzymes, transporters and many other proteins which constitute metabolism. Interactions of plants with their environment shape their growth, development and resilience towards adverse conditions. Although genome sequencing technologies and applications have experienced triumphantly rapid development during the last decades, enabling nowadays a fast and cheap sequencing of full genomes, prediction of metabolic phenotypes from genotype × environment interactions remains, at best, very incomplete.