Ferromagnetic Exchange and Slow Magnetic Relaxation in Cobalt Bis(1,2-dithiolene)-Bridged Dilanthanide Complexes.

The construction of multinuclear lanthanide-based molecules with significant magnetic exchange interactions represents a key challenge in the realization of single-molecule magnets with high operating temperatures. Here, we report the synthesis and magnetic characterization of two series of heterobimetallic compounds, (Cp*Ln)(μ-Co(pdt)) (Ln = Y, Gd, Dy; pdt = 1,2-diphenylethylenedithiolate) and [K(18-crown-6)][(Cp*Ln)(μ-Co(pdt))] (Ln = Y, Gd), featuring two lanthanide centers bridged by a cobalt bis(1,2-dithiolene) complex. Dc magnetic susceptibility data collected for the Gd congeners indicate significant Gd-Co ferromagnetic exchange interactions with fits affording = +11.

Heavy alcohol consumption but not smoking predicts mortality in patients with acute coronary syndrome.

The relationship of heavy alcohol consumption (HAC) and smoking to mortality in those with CHD, and mechanisms through which these effects are elicited are not clear. In order to improve our understanding, we examined the relationship of Alcohol T-Scores (ATS), an epigenetic biomarker of chronic HAC, and cg05575921 methylation, a biomarker of smoking intensity, with all-cause mortality and degree of coronary artery obstruction in a cohort of 217 subjects admitted for CHD-related acute coronary syndrome (ACS). We found that 65% of the subjects had ATS values indicative of chronic HAC.

An alternate synthetic pathway to nanoscopic LiFeS for energy storage.

Lithium-rich iron sulphide, LiFeS, exhibits reversible charge-storage both cationic and anionic sites, storing nearly 400 mA h g, but its synthesis is limited to solid-state methods that result in large primary particles. We describe an alternate solution-based, redox-mediated method to lithiate pyrite FeS, ultimately forming nanoscale LiFeS.

An Outline of a Simple, Interpretable Epigenetic Composite Score for Mortality Prediction for Accelerated Underwriting.

Background.—: In principle, it is generally accepted that DNA methylation measures can be used to predict mortality. However, as of yet, no epigenetic metric has been successfully incorporated into underwriting procedures.

High-temperature carbon dioxide capture in a porous material with terminal zinc hydride sites.

Carbon capture can mitigate point-source carbon dioxide (CO) emissions, but hurdles remain that impede the widespread adoption of amine-based technologies. Capturing CO at temperatures closer to those of many industrial exhaust streams (>200°C) is of interest, although metal oxide absorbents that operate at these temperatures typically exhibit sluggish CO absorption kinetics and instability to cycling. Here, we report a porous metal-organic framework featuring terminal zinc hydride sites that reversibly bind CO at temperatures above 200°C-conditions that are unprecedented for intrinsically porous materials.

Linear Inverse Sandwich Complexes of Tetraanionic Benzene Stabilized by Covalent δ-Bonding with Late Lanthanides.

A series of dilanthanide benzene inverse sandwich complexes of the type (CpLn)(μ-η:η-CH) () (Ln = Y, Gd, Tb, Dy, Tm) are reported. These compounds are synthesized by reduction of the respective trivalent dimers CpLnI (Ln = Y, Gd, Tb, Dy, Tm) in diethyl ether with potassium graphite in the presence of benzene, and they feature an unusual linear coordination geometry with a highly planar benzene bridge as verified by single-crystal X-ray diffraction. The Ln-Bz distances of are the shortest distances observed to date, ranging from 1.

Slow Magnetic Relaxation in a Californium Complex.

We report the synthesis and characterization of the macrocyclic californium derivative Na[Cf(HO)(DOTA)] (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), , which was studied in comparison to its dysprosium counterpart, Na[Dy(HO)(DOTA)], . Divergent spectroscopic and magnetic behaviors were observed between and . Based upon spectroscopic measurements, we propose that accessible 5f → 6d transitions (potentially operating in tandem with charge-transfer transitions) are the major contributors to the observed broadband photoluminescence in .

Long-Term Health Outcomes of Huntington Disease and the Impact of Future Disease-Modifying Treatments: A Decision-Modeling Analysis.

Background And Objectives: Disease-modifying treatments (DMTs) such as gene therapy are currently under investigation as a potential treatment for Huntington disease (HD). Our objective was to estimate the long-term natural history of HD progression and explore the potential efficacy impacts and value of a hypothetical DMT using a decision-analytic modeling framework.

Methods: We developed a health state transition model that separately analyzed 40-year-old individuals with prefunctional decline (PFD, HD Integrated Staging System [HD-ISS] stage <3, total functional score [TFC] 13), active functional decline Shoulson and Fahn category 1 (SF1, HD-ISS stage 3, TFC 13-11), and SF2 (HD-ISS stage 3, TFC 10-7).

Methylamine Separations Enabled by Cooperative Ligand Insertion in Copper-Carboxylate Metal-Organic Frameworks.

Monomethylamine (NHCH), dimethylamine (NH(CH)), and trimethylamine (N(CH)) are important chemical feedstocks that are produced industrially as an azeotropic mixture and must be separated using an energy-intensive thermal distillation. While solid adsorbents have been proposed as alternatives to distillation for separating various industrial gas mixtures, methylamine separations remain largely unexplored in this context. Here, we investigate two isoreticular frameworks Cu(cyhdc) (cyhdc = -1,4-cyclohexanedicarboxylate) and Cu(bdc) (bdc = 1,4-benzenedicarboxylate) as prospective candidates for this challenging separation, motivated by the recent discovery that Cu(cyhdc) reversibly captures ammonia through a unique framework-to-coordination polymer phase change.

Photocatalytic Extraction of Uranium from Seawater Using Covalent Organic Framework Nanowires.

In the push to achieve net-zero emissions by 2050, nuclear power will play an essential role alongside renewable wind and solar power, and correspondingly global interest and investment in this well-established technology is accelerating. The uranium present in seawater could support nuclear power generation for centuries, but traditional adsorptive separation strategies have proven ineffective for the selective extraction of uranium from this vast resource. Here, we report the synthesis of nanowires of a triazine-linked two-dimensional covalent organic framework via a solvent modulation approach, which can be used to access nanowire external diameters ranging from 50 to 200 nm.

Time to Functional Loss as an Endpoint in Huntington's Disease Trials: Enrichment and Sample Size.

Background: Clinical trial scenarios can be modeled using data from observational studies, providing critical information for design of real-world trials. The Huntington's Disease Integrated Staging System (HD-ISS) characterizes disease progression over an individual's lifespan and allows for flexibility in the design of trials with the goal of delaying progression. Enrichment methods can be applied to the HD-ISS to identify subgroups requiring smaller estimated sample sizes.

Exercise effects on brain health and learning from minutes to months: The brain EXTEND trial.

Despite evidence that aerobic exercise benefits the aging brain, in particular the hippocampus and memory, controlled clinical trials have not comprehensively evaluated effects of aerobic exercise training on human memory in older adults. The central goal of this study was to determine chronic effects of moderate-to-vigorous intensity aerobic exercise on the hippocampus and memory in non-demented, inactive adults ages 55-80 years. We determine effects of aerobic exercise training with a 6-month randomized controlled trial (RCT) comparing 150 min/week of home-based, light intensity exercise with progressive moderate-to-vigorous intensity aerobic exercise.

Geometric Tuning of Coordinatively Unsaturated Copper(I) Sites in Metal-Organic Frameworks for Ambient-Temperature Hydrogen Storage.

Porous solids can accommodate and release molecular hydrogen readily, making them attractive for minimizing the energy requirements for hydrogen storage relative to physical storage systems. However, H adsorption enthalpies in such materials are generally weak (-3 to -7 kJ/mol), lowering capacities at ambient temperature. Metal-organic frameworks with well-defined structures and synthetic modularity could allow for tuning adsorbent-H interactions for ambient-temperature storage.

Metal-Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp)UX (X = Cl, Br, I) Clusters.

The actinide elements are attractive alternatives to transition metals or lanthanides for the design of exchange-coupled multinuclear single-molecule magnets. However, the synthesis of such compounds is challenging, as is unraveling any contributions from exchange coupling to the overall magnetism. To date, only a few actinide compounds have been shown to exhibit exchange coupling and single-molecule magnetism.

Long-term transformational effects of near-death experiences.

Unlabelled: The purpose of this study was to deepen our understanding of the phenomenon of long-term transformational effects of near-death experiences (NDEs).

Methods: Participants included 834 individuals who had experienced NDEs. We compared their responses with those of 42 individuals who had faced life-threatening situations (LTEs) without experiencing NDEs, aiming to discern whether transformations could be attributed solely to the proximity to death.

Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (Cp)HoI.

Mixed-valence dilanthanide complexes of the type (Cp)LnI (Cp = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln-Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (Cp)LnI (; Ln = Ho, Er). Both compounds feature a Ln-Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er.

Long Duration Energy Storage Using Hydrogen in Metal-Organic Frameworks: Opportunities and Challenges.

Materials-based H storage plays a critical role in facilitating H as a low-carbon energy carrier, but there remains limited guidance on the technical performance necessary for specific applications. Metal-organic framework (MOF) adsorbents have shown potential in power applications, but need to demonstrate economic promises against incumbent compressed H storage. Herein, we evaluate the potential impact of material properties, charge/discharge patterns, and propose targets for MOFs' deployment in long-duration energy storage applications including backup, load optimization, and hybrid power.

Posttranscriptional regulation of by miR-124-3p at rs3512 underlies onset-delaying genetic modification in Huntington's disease.

Many Mendelian disorders, such as Huntington's disease (HD) and spinocerebellar ataxias, arise from expansions of CAG trinucleotide repeats. Despite the clear genetic causes, additional genetic factors may influence the rate of those monogenic disorders. Notably, genome-wide association studies discovered somewhat expected modifiers, particularly mismatch repair genes involved in the CAG repeat instability, impacting age at onset of HD.

Cerebellum Purkinje cell vulnerability in aged rats with memory impairment.

The cerebellum is involved in higher order cognitive function and is susceptible to age-related atrophy. However, limited evidence has directly examined the cerebellum's role in cognitive aging. To interrogate potential substrates of the relationship between cerebellar structure and memory in aging, here we target the Purkinje cells (PCs).

Understanding 2p core-level excitons of late transition metals by analysis of mixed-valence copper in a metal-organic framework.

The L-edge X-ray absorption spectra of late transition metals such as Cu, Ag, and Au exhibit absorption onsets lower in energy for higher oxidation states, which is at odds with the measured spectra of earlier transition metals. Time-dependent density functional theory calculations for Cu/Cu reveal a larger 2p core-exciton binding energy for Cu, overshadowing shifts in single-particle excitation energies with respect to Cu. We explore this phenomenon in a Cu metal-organic framework with ∼12% Cu defects and find that corrections with self-consistent excited-state total energy differences provide accurate XAS peak alignment.