Strategies to Calculate Fukui Functions and Applications to Radicals with SOMO-HOMO Inversion.

This work explores an efficient and numerically accurate procedure to obtain the Fukui function from fractional orbital occupation calculations. The energy- and density-linearity conditions are investigated in the context of using optimally tuned range-separated hybrid functionals for the calculation of the Fukui function. The methodology is then used to study the reactivity of organic radicals exhibiting energetic inversion between the singly occupied molecular orbital (SOMO) and the highest occupied molecular orbital (HOMO), that is, SOMO-HOMO inversion (SHI).

Insight into the Structural and Emissive Behavior of a Three-Dimensional Americium(III) Formate Coordination Polymer.

We report the structural, vibrational, and optical properties of americium formate (Am(CHO ) ) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am ions linked by formate ligands into a three-dimensional network that is isomorphous to several lanthanide analogs, (e. g.

Placental Inflammation Significantly Correlates with Reduced Risk for Retinopathy of Prematurity.

Retinopathy of prematurity (ROP), a blinding condition affecting preterm infants, is an interruption of retinal vascular maturation that is incomplete when born preterm. Although ROP demonstrates delayed onset following preterm birth, representing a window for therapeutic intervention, there are no curative or preventative measures available for this condition. The in utero environment, including placental function, is increasingly recognized for contributions to preterm infant disease risk.

A novel role for trithorax in the gene regulatory network for a rapidly evolving fruit fly pigmentation trait.

Animal traits develop through the expression and action of numerous regulatory and realizator genes that comprise a gene regulatory network (GRN). For each GRN, its underlying patterns of gene expression are controlled by cis-regulatory elements (CREs) that bind activating and repressing transcription factors. These interactions drive cell-type and developmental stage-specific transcriptional activation or repression.

Qualitative insights in item development for a comprehensive and inclusive measure of recovery capital.

Background: Item specification is foundational to measurement development but rarely reported in depth. We address this gap by explicating our use of qualitative methods to ground and develop items for a new recovery capital measure, the Multidimensional Inventory of Recovery Capital.

Method: We recruited a diverse sample of service providers ( = 9) and people in recovery from alcohol problems ( = 23) to provide feedback on an item pool assessing social, human, physical, community, and cultural capital.

Unified Description of Proton NMR Relaxation in Water, Acetonitrile, and Methane from Molecular Dynamics Simulations in the Liquid, Supercritical, and Gas Phases.

A comprehensive calculation of proton NMR relaxation in water, acetonitrile, and methane across a wide range of the phase diagram is provided via ab initio and force-field-based molecular dynamics simulations. The formalism used for the spin-rotation (SR) contribution to relaxation is developed for use with any molecular symmetry and utilizes the full molecular SR tensors, which are calculated from first-principles via Kohn-Sham (KS) DFT. In combination with calculations of the dipolar contribution, near-quantitative agreement with total measured relaxation rates is achieved.

Impact of community-based health insurance on health services utilisation among vulnerable households in Amhara region, Ethiopia.

Background: Ethiopia piloted community-based health insurance in 2011, and as of 2019, the programme was operating in 770 districts nationwide, covering approximately 7 million households. Enrolment in participating districts reached 50%, holding promise to achieve the goal of Universal Health Coverage in the country. Despite the government's efforts to expand community-based health insurance to all districts, evidence is lacking on how enrolment in the programme nudges health seeking behaviour among the most vulnerable rural households.

Reporter gene assays and chromatin-level assays define substantially non-overlapping sets of enhancer sequences.

Background: Transcriptional enhancers are essential for gene regulation, but how these regulatory elements are best defined remains a significant unresolved question. Traditional definitions rely on activity-based criteria such as reporter gene assays, while more recently, biochemical assays based on chromatin-level phenomena such as chromatin accessibility, histone modifications, and localized RNA transcription have gained prominence.

Results: We examine here whether these two types of definitions, activity-based and chromatin-based, effectively identify the same sets of sequences.

FOXA1/2 depletion drives global reprogramming of differentiation state and metabolism in a human liver cell line and inhibits differentiation of human stem cell-derived hepatic progenitor cells.

FOXA factors are critical members of the developmental gene regulatory network (GRN) composed of master transcription factors (TF) which regulate murine cell fate and metabolism in the gut and liver. How FOXA factors dictate human liver cell fate, differentiation, and simultaneously regulate metabolic pathways is poorly understood. Here, we aimed to determine the role of FOXA2 (and FOXA1 which is believed to compensate for FOXA2) in controlling hepatic differentiation and cell metabolism in a human hepatic cell line (HepG2).

Repurposed dihydroorotate dehydrogenase inhibitors with efficacy against drug-resistant .

New antimicrobials are needed for the treatment of extensively drug-resistant . The de novo pyrimidine biosynthetic enzyme dihydroorotate dehydrogenase (DHODH) is a validated drug target for malaria and human autoimmune diseases. We provide genetic evidence that DHODH (DHODH) is essential for bacterial survival in rodent infection models.

Knowledge of and access to frontline workers among poor, rural households in Amhara region, Ethiopia: a mixed-methods study.

Background: Social protection programmes have effectively reduced poverty and improved food security. However, the effects of poverty require an intersectoral approach to adequately address poor nutrition and health. Identifying gaps in knowledge and access to frontline workers who oversee these integrations is critical for understanding the potential for integrated social protection programming to improve these outcomes.

A reversal of the song advantage in vocal pitch imitation.

Previous experiments have documented an advantage for vocal pitch-matching when participants sing back a short melody, in contrast to when participants attempt to imitate the pitch contour of spoken English. These results appear to confirm recent claims that music involves greater precision of pitch than speech. A re-analysis of these data is reported here that focuses on imitation of pitch trajectories within sung notes or spoken syllables.

Do Neighborhood Factors Modify the Effects of Lead Exposure on Child Behavior?

Lead exposure and neighborhoods can affect children’s behavior, but it is unclear if neighborhood characteristics modify the effects of lead on behavior. Understanding these modifications has important intervention implications. Blood lead levels (BLLs) in children (~7 years) from Montevideo, Uruguay, were categorized at 2 µg/dL.

Cognitive Relapse in Multiple Sclerosis: New Findings and Directions for Future Research.

Multiple sclerosis (MS) is a chronic inflammatory, demyelinating disease of the central nervous system, often presenting with brain atrophy and cognitive impairment (CI). In the relapsing-remitting phenotype, cognitive performance is increasingly recognized to decline acutely during MS relapse, with varying degrees of recovery afterwards. Therefore, CI in MS may result from incomplete recovery from episodes of so-called "cognitive relapse", gradual neurodegeneration, or both.

Effects of COVID-19 lockdown on lifestyle behaviors in children with obesity: Longitudinal study update.

Objective: A previous report from our group identified directionally unfavorable dietary and lifestyle behavior trends in longitudinally monitored children and adolescents with obesity early in the COVID-19 pandemic lockdown. The current study aimed at extending these previous observations in youths with obesity on the dietary and lifestyle behavioral consequences of the extended COVID-19 lockdown in Verona, Italy.

Methods: The sample included 32 children and adolescents with obesity participating in the longitudinal OBELIX study.

Bench-Stable Dinuclear Mn(I) Catalysts in E-Selective Alkyne Semihydrogenation: A Mechanistic Investigation.

Dinuclear manganese hydride complexes of the form [Mn (CO) (μ-H)(μ-PR )] (R=Ph, 1; R=iPr, 2) were used in E-selective alkyne semi-hydrogenation (E-SASH) catalysis. Catalyst speciation studies revealed rich coordination chemistry and the complexes thus formed were isolated and in turn tested as catalysts; the results underscore the importance of dinuclearity in engendering the observed E-selectivity and provide insights into the nature of the active catalyst. The insertion product obtained from treating 2 with (cyclopropylethynyl)benzene contains a cis-alkenyl bridging ligand with the cyclopropyl ring being intact.

Np Mössbauer Isomer Shifts: A Lesson About the Balance of Static and Dynamic Electron Correlation in Heavy Element Complexes.

A large set of neptunium compounds with different oxidation states (III to VII) was assembled to study the Mössbauer isomer shift by wave function calculations and better understand covalency in f-elements complexes. The contact density approach was used to calculate the isomer shift using complete active space self-consistent field (CASSCF) multiconfiguration wave functions, as well as matrix product states [from Density Matrix Renormalization Group (DMRG) algorithms] for large active spaces. Dynamic correlation effects for the isomer shifts were treated via CASPT2 energy derivatives with respect to the nuclear radius.

Covalency in actinide(iv) hexachlorides in relation to the chlorine K-edge X-ray absorption structure.

Chlorine K-edge X-ray absorption near edge structure (XANES) in actinide hexachlorides, [AnCl] (An = Th-Pu), is calculated with relativistic multiconfiguration wavefunction theory (WFT). Of particular focus is a 3-peak feature emerging from U toward Pu, and its assignment in terms of donation bonding to the An 5f 6d shells. With or without spin-orbit coupling, the calculated and previously measured XANES spectra are in excellent agreement with respect to relative peak positions, relative peak intensities, and peak assignments.

Common Themes and Future Challenges in Understanding Gene Regulatory Network Evolution.

A major driving force behind the evolution of species-specific traits and novel structures is alterations in gene regulatory networks (GRNs). Comprehending evolution therefore requires an understanding of the nature of changes in GRN structure and the responsible mechanisms. Here, we review two insect pigmentation GRNs in order to examine common themes in GRN evolution and to reveal some of the challenges associated with investigating changes in GRNs across different evolutionary distances at the molecular level.

A deep learning model for burn depth classification using ultrasound imaging.

Identification of burn depth with sufficient accuracy is a challenging problem. This paper presents a deep convolutional neural network to classify burn depth based on altered tissue morphology of burned skin manifested as texture patterns in the ultrasound images. The network first learns a low-dimensional manifold of the unburned skin images using an encoder-decoder architecture that reconstructs it from ultrasound images of burned skin.

Spatiotemporal imaging and analysis of mouse and human liver bud morphogenesis.

Background: The process of liver organogenesis has served as a paradigm for organ formation. However, there remains a lack of understanding regarding early mouse and human liver bud morphogenesis and early liver volumetric growth. Elucidating dynamic changes in liver volumes is critical for understanding organ development, implementing toxicological studies, and for modeling hPSC-derived liver organoid growth.

Linking poverty-targeted social protection and Community Based Health Insurance in Ethiopia: Enrolment, linkages, and gaps.

Background: Community-Based Health Insurance (CBHI) has received increasing attention in low and middle-income countries as a pathway toward universal health coverage. In 2011, the government of Ethiopia piloted CBHI and subsequently integrated CBHI with its flagship social protection programme, the Productive Safety Net Program (PSNP) which was established in 2005. We examined enrolment decisions by PSNP households, including, understanding of the programme, reasons for non-coverage, and factors associated with enrolment decisions.