10-Fold Increase in Hydrogen Atom Transfer Reactivity for a Series of = 1 Fe═O Complexes Over the = 2 [(TQA)Fe═O] Complex via Entropic Lowering of Reaction Barriers by Secondary Sphere Cycloalkyl Substitution.

Nonheme iron enzymes utilize = 2 iron(IV)-oxo intermediates as oxidants in biological oxygenations. In contrast, corresponding synthetic nonheme Fe═O complexes characterized to date favor the = 1 ground state that generally shows much poorer oxidative reactivity than their = 2 counterparts. However, one intriguing exception found by Nam a decade ago is the = 1 [Fe(O)(MeNTB)] complex (MeNTB = [tris((-methyl-benzimidazol-2-yl)methyl)amine], ) with a hydrogen atom transfer (HAT) reactivity that is 70% that of the = 2 [Fe(O)(TQA)] complex (TQA = tris(2-quinolylmethyl)amine, ).

Long Sleep Duration, Cognitive Performance, and the Moderating Role of Depression: A Cross-Sectional Analysis in the Framingham Heart Study.

Introduction: We investigated whether depression modified the associations between sleep duration and cognitive performance.

Methods: Multivariable linear regression models examined the associations between sleep duration and cognition in 1,853 dementia- and stroke-free participants from the Framingham Heart Study. Participants were categorized in four groups: no depressive symptoms, no antidepressants; depressive symptoms without antidepressants use; antidepressant use without depressive symptoms; both depressive symptoms and antidepressant use.

Neutrophil prime unique transcriptional responses in intestinal organoids during infection with nontyphoidal serovars.

Nontyphoidal strains of are a major cause of foodborne illnesses, and infection with these bacteria results in inflammatory gastroenteritis. Polymorphonuclear leukocytes (PMNs), also known as neutrophils, are a dominant immune cell type found at the site of infection in infected individuals, but how they regulate infection outcome is not well understood. Here, we used a co-culture model of primary human PMNs and human intestinal organoids to probe the role of PMNs during infection with two of the most prevalent serovars: serovar Enteritidis and Typhimurium.

Why Symptoms Linger in Quiescent Crohn's Disease: Investigating the Impact of Sulfidogenic Microbes and Sulfur Metabolic Pathways.

Introduction: Even in the absence of inflammation, persistent symptoms in patients with Crohn's disease (CD) are prevalent and worsen quality of life. We previously demonstrated enrichment in sulfidogenic microbes in quiescent Crohn's disease patients with (qCD + S) vs without persistent GI symptoms (qCD-S). Thus, we hypothesized that sulfur metabolic pathways would be enriched in stool while differentially abundant microbes would be associated with important sulfur metabolic pathways in qCD + S.