Under most conditions, 2,4-dihalopyrimidines undergo substitution reactions at C4. Here we report that Pd(II) precatalysts supported by bulky -heterocyclic carbene ligands uniquely effect C2-selective cross-coupling of 2,4-dichloropyrimidine with thiols. The regioselectivity of this reaction stands in stark contrast to ∼1500 previously reported Pd-catalyzed cross-couplings that favor C4 in the absence of other substituents on the pyrimidine ring.
View Article and Find Full Text PDFTargeting Ru(III) and Ru(I) η-alkyne species, 2,2'-(PrE)-substituted diphenylacetylenes (1-E, E=P, As) were employed for the preparation of [ECCE]-coordinated ruthenium complexes. The reactions between 1-E and cis-(MeCN)(COD)RuCl led to the required Ru(II) starting materials cis-[ECCE]RuCl(MeCN) (3-E). Upon oxidation of 3-E with PhICl, the Ru(III) target complexes [ECCE]RuCl (7-E) were detectable for E=P and E=As, but only the arsa-derivative 7-As was obtained in a pure form, namely via oxidation of cis-[AsCCAs]RuCl(THT) (THT=tetrahydrothiophene).
View Article and Find Full Text PDFWe and others previously found that a misannotated long noncoding RNA encodes for a conserved mitochondrial transmembrane microprotein named Mitoregulin (Mtln). Beyond an established role for Mtln in lipid metabolism, Mtln has been shown to broadly influence mitochondria, boosting respiratory efficiency and Ca retention capacity, while lowering ROS, yet the underlying mechanisms remain unresolved. Prior studies have identified possible Mtln protein interaction partners; however, a lack of consensus persists, and no claims have been made about Mtln's structure.
View Article and Find Full Text PDFBackground: Despite the immense impact of Long COVID on public health and those affected, its aetiology remains poorly understood. Findings suggest that psychological factors such as depression contribute to symptom persistence alongside pathophysiological mechanisms, but knowledge of their relative importance is limited. This study aimed to synthesise the current evidence on psychological factors potentially associated with Long COVID and condition-relevant outcomes like quality of life.
View Article and Find Full Text PDFVertebrate vision in dim-light environments is initiated by rod photoreceptor cells that express the photopigment rhodopsin, a G-protein coupled receptor (GPCR). To ensure efficient light capture, rhodopsin is densely packed into hundreds of membrane discs that are tightly stacked within the rod-shaped outer segment compartment. Along with its role in eliciting the visual response, rhodopsin serves as both a building block necessary for proper outer segment formation as well as a trafficking guide for a few outer segment resident membrane proteins.
View Article and Find Full Text PDFPatients with rheumatoid arthritis (RA) have increased hypertension. Tissue sodium may contribute to development and progression of hypertension through immune cell activation. This study aimed to determine if skin sodium content is: 1) higher in RA versus control participants, and 2) associated with blood pressure and disease activity.
View Article and Find Full Text PDFBackground: Tuberculosis vaccine trials using disease as the primary endpoint are large, time consuming, and expensive. An earlier immunological measure of the protection against disease would accelerate tuberculosis vaccine development. We aimed to assess whether the effectiveness of the Bacillus Calmette-Guérin (BCG) vaccine for prevention of Mycobacterium tuberculosis infection was consistent with that for prevention of tuberculosis disease.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Despite the prominence of C-N bond forming cross-coupling reactions as a strategy to assemble molecular fragments, aminative coupling approaches, in which two fragments are assembled directly at the heteroatom, represents a rarely exploited retrosynthetic strategy. Herein, we report the design, synthesis, and implementation of an anomeric amide reagent capable of promoting highly regioselective aminative alkene-arene and alkene-alkene coupling reactions. This transformation follows a sequence of catalyst-free chloroamination, N-deprotection, and formal nitrene functionalization, all in one-pot.
View Article and Find Full Text PDFBackground: Female homicides are a public health-relevant issue, and its spatial distribution may evidence socioeconomic vulnerabilities. This study aims to analyze the temporal and spatial trends of female homicides in Brazil and investigate socioeconomic-demographic factors associated with it.
Methods: This is an ecological, descriptive, and analytical epidemiological study investigating the age-standardized female homicide rate in all Brazilian municipalities between 2000 and 2018, divided into three periods.
Objectives: Analyze the burden of diseases attributable to risk factors (RF) in Brazil according to age, sex, and Brazilian states between 1990 and 2021.
Methods: This study used data from the Global Burden of Disease study 1990 to 2021. The metrics used in this analysis included: mortality rates, disability-adjusted life years (DALYs) and Summary Exposure Value (SEV).
Large self-assembled systems (such as metallosupramolecular rings and cages) can be difficult to structurally characterize, in particular when they show a highly dynamic behavior. In the gas-phase, Ion Mobility Spectrometry (IMS), in tandem with Electrospray Ionization Mass Spectrometry (ESI MS), can yield valuable insights into the size, shape and dynamics of such supramolecular assemblies. However, the detailed relationship between experimental IMS data and the actual gas-phase structure is still poorly understood for soft and flexible self-assemblies.
View Article and Find Full Text PDFOur study investigates the effectiveness of Oxford Nanopore Technologies for accurate outbreak tracing by resequencing 33 isolates of a 3-year-long outbreak with Illumina short-read sequencing data as the point of reference. We detect considerable base errors through cgMLST and phylogenetic analysis of genomes sequenced with Oxford Nanopore Technologies, leading to the false exclusion of some outbreak-related strains from the outbreak cluster. Nearby methylation sites cause these errors and can also be found in other species besides Based on these data, we explore PCR-based sequencing and a masking strategy, which both successfully address these inaccuracies and ensure accurate outbreak tracing.
View Article and Find Full Text PDFConspecific density dependence (CDD) in plant populations is widespread, most likely caused by local-scale biotic interactions, and has potentially important implications for biodiversity, community composition, and ecosystem processes. However, progress in this important area of ecology has been hindered by differing viewpoints on CDD across subfields in ecology, lack of synthesis across CDD-related frameworks, and misunderstandings about how empirical measurements of local CDD fit within the context of broader ecological theories on community assembly and diversity maintenance. Here, we propose a conceptual synthesis of local-scale CDD and its causes, including species-specific antagonistic and mutualistic interactions.
View Article and Find Full Text PDFBackground: Simulation assessment can result in anxiety for students. These assessments involve being observed by assessors, so there is a significant socio-evaluative stress component which may cause greater anxiety if assessors are visible to students during assessments. The aim of this study was to determine the effect of assessor visibility on biological and physiological markers of stress and levels of anxiety experienced by pre-hospital emergency care students in a simulation assessment environment.
View Article and Find Full Text PDFThis article aims to estimate the underreporting of violence against women (VAW) in the Notifiable Diseases Information System (SINAN), based on data from the National Survey of Health (NSH), in Brazil and subnational units (SU). This work was an ecological study using SINAN and NSH, both from 2019. In SINAN, reports of sexual, physical, and psychological VAW, aged 18 years or older, were selected.
View Article and Find Full Text PDFBackground: The COVID-19 pandemic and response severely impacted people living with non-communicable diseases (PLWNCDs) globally. It exacerbated pre-existing health inequalities, severely disrupted access to care, and worsened clinical outcomes for PLWNCDs, who were at higher risk of morbidity and mortality from the virus. The pandemic's effects were likely magnified in humanitarian settings, where there were pre-existing gaps in continuity of care for non-communicable diseases (NCDs).
View Article and Find Full Text PDFJ Child Adolesc Psychopharmacol
November 2024
Autistic youth are more likely to experience maltreatment, victimization, and other traumatic events. However, it can be difficult to identify trauma-related symptoms in autistic youth, especially in those with limited verbal communication. In this study, we compared the prevalence of trauma-related diagnoses given to youth with autism spectrum disorder (ASD) to those given to youth without ASD who presented to a specialized pediatric psychiatric emergency department.
View Article and Find Full Text PDFBackground: Fencing is a unique and increasingly popular sport, but limited data exist regarding related injuries.
Purpose: To examine the types of injuries incurred by fencing athletes, and to analyze associations between age, sex, and hand dominance with type and location of injury.
Study Design: Cross-sectional.
Background Medical educators face many challenges, including the absence of defined roles, lack of standard career paths, and limited support in systems that generally prioritize research and clinical productivity over educational activities. Providers also teach to widely varying degrees. This study was designed to specifically examine the professional rewards and obstacles experienced by physicians who have dedicated significant energy and career focus to medical education.
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