Regioselective 1,4-Addition of P(O)-H Species to In SituFormed 1-Benzopyrylium Ion from C3-Substituted 2-Chromene Hemiketals to Construct C3-Functionalized C4-Phosphorylated 4-Chromenes.

Herein, we report the first example that P(O)-H species including -phosphonates and -phosphine oxides could participate in a highly regioselective 1,4-addition to in situ generated 1-benzopyrylium ion from C3-substituted 2-chromene hemiketals, which provides a brand-new and effective approach for the synthesis of C4-phosphorylated 4-chromenes with diverse C3-functionality (ketone, ester, sulfonyl, aryl, and alkyl groups). In total, the reaction features the use of inexpensive Zn(ClO)·6HO as a catalyst, low catalyst loading (only 5 mol %), mild reaction conditions (60 °C, 10 min to 24 h), and broad substrate scope (46 examples) as well as good to high yields (>90% yield on average). More importantly, mechanistic experiments demonstrated the essential role of the C3-substituent on 2-chromene hemiketals in stabilizing the in situ generated 1-benzopyrylium ion and the regioselective 1,4-addition control.

Associations between 25-hydroxyvitamin D/calcium/alkaline phosphatase levels and the risk of developing kidney stones: Results from NHANES (2013-2018)-based and Mendelian randomization studies.

This study explores the relationship between 25-hydroxyvitamin D/calcium/alkaline phosphatase (ALP) levels and kidney stone development via cross-sectional and Mendelian randomization (MR) analyses. We used data from the National Health and Nutrition Examination Survey (NHANES) 2013 to 2018 to explore the associations of 25(OH)D metabolite, calcium, and ALP levels with kidney stone development, LDSC analysis to determine the associations between their genetically predicted levels and kidney stone development, and MR analysis to determine the causality of those relationship via genome-wide association studies (GWASs). The cross-sectional study revealed a relationship between ALP levels and kidney stone development (Model 1: OR = 1.

Lewis Base-Enhanced C-H Bond Functionalization Mediated by a Diiron Imido Complex.

Herein, we investigate the effects of ligand design on the nuclearity and reactivity of metal-ligand multiply bonded (MLMB) complexes to access an exclusively bimetallic reaction pathway for C-H bond functionalization. To this end, the diiron alkoxide [Fe(Dbf)] () was treated with 3,5-bis(trifluoromethyl)phenyl azide to access the diiron imido complex [Fe(Dbf)(μ-NCHF)] () that promotes hydrogen atom abstraction (HAA) from a variety of C-H and O-H bond containing substrates. A diiron bis(amide) complex [Fe(Dbf)(μ-NHCHF)(NHCHF)] () was generated, prompting the isolation of the analogous bridging amide terminal alkoxide [Fe(Dbf)(μ-NHCHF)(OCH)] () and the asymmetric pyridine-bound diiron imido [Fe(Dbf)(μ-NCHF)(NCH)] ().

Electron density distribution in bis(guanidinium) disodium hypodiphosphate heptahydrate, (CHN)Na(PO)·7HO.

X-ray structural analysis of bis(guanidinium) disodium hypodiphosphate heptahydrate, (CHN)Na(PO)·7HO revealed close Na...

Impact of vitamin D supplementation on symptom severity and quality of life in patients with irritable bowel syndrome: A meta-analysis.

Background: Vitamin D supplementation could offer irritable bowel syndrome (IBS) patients significant improvements in terms of symptom severity and overall quality of life (QoL). Yet, the potential benefits and risks associated with vitamin D supplementation still require additional investigation.

Objectives: We aimed to evaluate the impact of vitamin D supplementation on IBS using a systematic review and meta-analysis.

Altered Effective Connectivity Within a Thalamocortical Corollary Discharge Network in Individuals With Schizophrenia.

Background And Hypothesis: Sequential saccade planning requires corollary discharge (CD) signals that provide information about the planned landing location of an eye movement. These CD signals may be altered among individuals with schizophrenia (SZ), providing a potential mechanism to explain passivity and anomalous self-experiences broadly. In healthy controls (HC), a key oculomotor CD network transmits CD signals from the thalamus to the frontal eye fields (FEF) and the intraparietal sulcus (IPS) and also remaps signals from FEF to IPS.

Regulating Charge Distribution in Porphyrin-Based Polymer for Achieving Photocatalytic CO Conversion to CH or CH.

The photocatalytic conversion of CO into products such as CH and CH poses a significant challenge due to the lengthy reaction steps and the high energy barrier involved. In this study, both benzothiadiazole (BTD) and hydroxyl groups (-OH) are introduced into cobalt-based polymerized porphyrinic network (PPN) through a C-C coupling reaction. This modification of orbital energy levels that strengthens the ability of gain electrons and facilitates the charge transfer in PPN.

Direct Observation of Substantial Phonon Nonequilibrium Near Nanoscale Hotspots in Gallium Nitride.

Phonon modal nonequilibrium is believed to widely exist around nanoscale hotspots, which can significantly affect the performance of nano-electronic and optoelectronic devices. However, such a phenomenon has not been explicitly observed in 3D device semiconductors at the nanoscale. Here, by employing a tip-enhanced Raman thermal measurement approach, substantial phonon nonequilibrium in gallium nitride near sub-10 nm laser-excited hotspots is directly revealed for the first time.

Flexible Synaptic Memristors With Controlled Rigidity in Zirconium-Oxo Clusters for High-Precision Neuromorphic Computing.

Flexible memristors are promising candidates for multifunctional neuromorphic computing applications, overcoming the limitations of conventional computing devices. However, unpredictable switching behavior and poor mechanical stability in conventional memristors present significant challenges to achieving device reliability. Here, a reliable and flexible memristor using zirconium-oxo cluster (ZrOOH(OMc)) as the resistive switching layer is demonstrated.

Degradation of Methylene Blue by Ozone Oxidation Catalyzed by the Magnetic MnFeO@CoS Nanocomposite.

In this study, the MnFeO@CoS magnetic nanocomposite was prepared by a two-step hydrothermal method and used to catalyze the ozone oxidation degradation of methylene blue. It was characterized by XRD, EDS, SEM, FT-IR, and XPS. The results showed that the introduction of CoS made MnFeO grow uniformly on CoS nanosheets, which effectively prevented the agglomeration of MnFeO.

Tau Pathology Drives Disease-Associated Astrocyte Reactivity in Salt-Induced Neurodegeneration.

Dietary high salt intake is increasingly recognized as a risk factor for cognitive decline and dementia, including Alzheimer's disease (AD). Recent studies have identified a population of disease-associated astrocytes (DAA)-like astrocytes closely linked to amyloid deposition and tau pathology in an AD mouse model. However, the presence and role of these astrocytes in high-salt diet (HSD) models remain unexplored.

Electrooxidation of Ethylene Glycol to Glycolic Acid with Pt-Ni(OH)2 Catalysts: High Efficiency and Selectivity for PET Plastics Upgrading.

The electroconversion of polyethylene terephthalate (PET) into C2 fine chemicals and hydrogen (H2) presents a promising solution for advancing the circular plastics economy. In this study, we report the electrooxidation of ethylene glycol (EG) to glycolic acid (GA) using a Pt-Ni(OH)2 catalyst, achieving a high Faraday efficiency (>90%) even at high current densities (250 mA cm-2 at 0.8 V vs.

Comprehensive Characterization of Overt Myelofibrosis in an Asian Cohort: Phenotype, Mutation Landscape and Discordance Among Scoring Systems.

Various prognostic scoring systems in myelofibrosis (MF) have been developed to guide clinical decision-making in MF. However, discrepancies between different scoring systems for individual patients remain poorly understood, which can result in conflicting treatment recommendations. Moreover, data regarding there applicability in Asian populations remain scarce.

Aging Concerns Related to Sexuality and Gender: HIV Prevention and Healthy Aging.

Healthy aging is an important area of research across many populations, but less work has focused on this area among sexual and gender diverse individuals relative to the general population. On the whole, it is known that as the U.S.

Exploring timely and safe discharge from ICU: a comparative study of machine learning predictions and clinical practices.

Background: The discharge practices from the intensive care unit exhibit heterogeneity and the recognition of eligible patients for discharge is often delayed. Recognizing the importance of safe discharge, which aims to minimize readmission and mortality, we developed a dynamic machine-learning model. The model aims to accurately identify patients ready for discharge, offering a comparison of its effectiveness with physician decisions in terms of safety and discrepancies in discharge readiness assessment.

Demographic and Experiential Characteristics of Asexual Individuals and Associations with Well-Being.

The visibility and number of people identifying as asexual-those with little to no sexual attraction-have been increasing in recent years. In the current study, we examined variation in experiential and developmental milestones and psychosocial functioning in 1,726 individuals on the asexual spectrum (61.2% women, 15.

Increased stiffness with medial column screw supplementation of lateral locking plate for distal femur fractures: a biomechanical study.

Introduction: We propose and assess the biomechanical stability of medial column screw supplementation in a synthetic distal femur fracture model.

Materials And Methods: Twenty-four low density synthetic femora modeling osteoporotic, intraarticular distal femur fractures with medial metaphyseal comminution were split into two fixation groups: (1) lateral locking distal femur plate (PA- plate alone) and (2) lateral locking distal femur plate with a 6.5 mm fully threaded medial cannulated screw (PWS- plate with screw).

A multivariable prediction model for invasive pulmonary aspergillosis in immunocompromised patients with acute respiratory failure (IPA-GRRR-OH score).

Purpose: Invasive pulmonary aspergillosis (IPA) is a life-threatening opportunistic infection in immunocompromised patients. The diagnosis is often made late, with mortality reaching 90% when mechanical ventilation is needed. We sought to develop and validate a risk prediction model for the diagnosis of IPA.

Role of Heterogeneous Reactions in the Atmospheric Oxidizing Capacity in Island Environments.

The source of nitrous acid (HONO) and its importance in island or marine environments are poorly understood. Herein, based on comprehensive field measurements at a hilltop on Corsica Island, we find an inverse diel variation of HONO with higher concentrations during daytime. Night-time HONO budget analysis indicates significant HONO formation during air mass transport along the hillside.

Neural mechanisms of behavioral addiction: An ALE meta-analysis and MACM analysis.

Background And Aims: Behavioral addictions (BAs) represent complex and multifaceted disorders often associated with maladaptive neural alteration. To deepen our understanding of the essence of BAs, this study focuses on the neural mechanisms underlying its three stages: reward seeking, self-control, and decision-making. The aim of the current meta-analysis is to investigate the brain regions and neural networks involved in BAs.

Acute Effects of a Single Bout of Strength and Endurance Exercise on Vitamin D Metabolites in Young Adults.

Purpose: The effect of exercise on serum concentration of vitamin D metabolites remains inconclusive, with studies reporting deviating results. This study evaluated the acute effect of a single session of two specific exercise forms; strength training (ST) and high-intensity interval training (HIIT), on circulating 25-hydroxyvitamin D (25(OH)D), free25(OH)D and 1,25-dihydroxyvitamin D (1,25(OH)2D), and skeletal muscle vitamin D receptor (VDR) gene expression, in healthy adults.

Methods: Thirty-nine participants (19 women and 20 men, age 21-30 years) completed a single bout of ST and HIIT exercise, separated by two weeks.

Cutaneous dysbiosis characterizes the post-allogeneic hematopoietic stem cell transplantation period.

Gut dysbiosis is linked to mortality and the development of graft-versus-host disease (GVHD) after hematopoietic stem cell transplantation (HSCT), but the impact of cutaneous dysbiosis remains unexplored. We performed a pilot observational study and obtained retroauricular and forearm skin swabs from 12 adult patients prior to conditioning chemotherapy/radiation, and at 1-week, 1-month and 3-months after allogeneic HSCT, and performed shotgun metagenomic sequencing. The cutaneous microbiome among HSCT patients was enriched for gram-negative bacteria such as E coli and Pseudomonas, fungi, and viruses.

Circulating and Magnetic Resonance Imaging Biomarkers of Intestinal Fibrosis in Small Bowel Crohn's Disease.

Background: We previously identified circulating and MRI biomarkers associated with the surgical management of Crohn's disease (CD). Here we tested associations between these biomarkers and ileal resection inflammation and collagen content.

Methods: Fifty CD patients undergoing ileal resection were prospectively enrolled at 4 centers.

Lessons Learned in Virtual Launch of an Antenatal Opioid Exposure Study During the COVID-19 Pandemic.

Background: The COVID-19 pandemic prompted researchers to develop new ways to design and launch studies and recruit and retain participants. Pregnant women and infants are considered vulnerable populations in research, and families affected by substance use are particularly difficult to recruit and retain. Recruitment for studies involving medical technologies such as MRI can also be difficult due to misconceptions and fear of the technologies.

Specialty laboratory testing for chronic abdominal pain in irritable bowel syndrome.

Background: Irritable bowel syndrome (IBS) is a common gastrointestinal disorder seen by both primary care providers (PCPs) and gastroenterologists, and further diagnostic testing is generally discouraged unless red-flag symptoms are present.

Aims: Examine if advanced serologic testing for chronic abdominal pain in IBS patients followed society-specific guidelines and evaluate the diagnostic accuracy of these tests.

Methods: The study involved a retrospective cross-sectional analysis of adults aged 18 and older who were seen at our institution between 2013 and 2018.