Synergistic Steric and Electronic Effects on the Photoredox Catalysis by a Multivariate Library of Titania Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) that display photoredox activity are attractive materials for sustainable photocatalysis. The ability to tune both their pore sizes and electronic structures based solely on the choice of the building blocks makes them amenable for systematic studies based on physical organic and reticular chemistry principles with high degrees of synthetic control. Here, we present a library of eleven isoreticular and multivariate (MTV) photoredox-active MOFs, UCFMOF-n, and UCFMTV-n-x% with a formula Ti6O9[links]3, where the links are linear oligo-p-arylene dicarboxylates with n number of p-arylene rings and x mol% of multivariate links containing electron-donating groups (EDGs). The average and local structures of UCFMOFs were elucidated from advanced powder X-ray diffraction (XRD) and total scattering tools, consisting of parallel arrangements of one-dimensional (1D) [Ti6O9(CO2)6]∞ nanowires connected through the oligo-arylene links with the topology of the edge-2-transitive rod-packed hex net. Preparation of an MTV library of UCFMOFs with varying link sizes and amine EDG functionalization enabled us to study both their steric (pore size) and electronic (highest occupied molecular orbital-lowest unoccupied molecular orbital, HOMO-LUMO, gap) effects on the substrate adsorption and photoredox transformation of benzyl alcohol. The observed relationship between the substrate uptake and reaction kinetics with the molecular traits of the links indicates that longer links, as well as increased EDG functionalization, exhibit impressive photocatalytic rates, outperforming MIL-125 by almost 20-fold. Our studies relating photocatalytic activity with pore size and electronic functionalization demonstrate how these are important parameters to consider when designing new MOF photocatalysts.

Sports- and Physical Activity-Related Concussions, Binge Drinking and Marijuana Use among Adolescents: The Mediating Role of Depression and Suicidal Ideation.

BACKGROUND: Although past studies have examined the adverse impact of sports- and physical activity-related concussions (SPACs) on health and mental health outcomes, there is a dearth of research investigating the association between SPACs and binge drinking and marijuana use. OBJECTIVE: The objective of this study is to examine the cross-sectional association between SPACs and binge drinking and marijuana use among adolescents and whether symptoms of depression and suicidal ideation mediate this association. METHODS: Data for this study came from the 2017 and 2019 National Youth Risk Behavior Survey. An analytic sample of 17,175 adolescents aged 14-18 years (50.2% male) was analyzed using binary logistic regression. RESULTS: Of the 17,175 adolescents, 13.7% engaged in binge drinking and 19.3% used marijuana 30 days preceding the survey date. Approximately one in seven (14.1%) adolescents had SPACs during the past year. Upon controlling for the effects of other factors, adolescents who had SPACs had 1.74 times higher odds of engaging in binge drinking (AOR = 1.74, p<.001, 95% CI = 1.47-2.06) and 1.42 times higher odds of using marijuana (AOR = 1.42, p<.001, 95% CI = 1.24-1.62) than those who did not have SPACs. Symptoms of depression and suicidal ideation explained 12% of the association between SPACs and binge drinking, and 19% of the association between SPACs and marijuana use. CONCLUSIONS: Understanding the association between SPACs and substance use and mental health could contribute to early identification of adolescents who may engage in substance use.

Mechanically Shaped Two-Dimensional Covalent Organic Frameworks Reveal Crystallographic Alignment and Fast Li-Ion Conductivity.

Covalent organic frameworks (COFs) usually crystallize as insoluble powders, and their processing for suitable devices is thought to be limited. We demonstrate that COFs can be mechanically pressed into shaped objects having anisotropic ordering with preferred orientation between hk0 and 00l crystallographic planes. Five COFs with different functionality and symmetry exhibited similar crystallographic behavior and remarkable stability, indicating the generality of this processing. Pellets prepared from bulk COF powders impregnated with LiClO4 displayed room temperature conductivity up to 0.26 mS cm(-1) and high electrochemical stability. This outcome portends use of COFs as solid-state electrolytes in batteries.

History of incarceration and age-related neurodegeneration: Testing models of genetic and environmental risks in a longitudinal panel study of older adults.

History of incarceration is associated with an excess of morbidity and mortality. While the incarceration experience itself comes with substantive health risks (e.g., injury, psychological stress, exposure to infectious disease), most individuals eventually return from prison to the general population where they will be diagnosed with the same age-related conditions that drive mortality in the non-incarcerated population but at exaggerated rates. However, the interplay between history of incarceration as a risk factor and more traditional risk factors for age-related diseases (e.g., genetic risk factors) has not been studied. Here, we focus on cognitive impairment, a hallmark of neurodegenerative conditions like Alzheimer's disease, as an age-related state that may be uniquely impacted by the confluence of environmental stressors (e.g., incarceration) and genetic risk factors. Using data from the Health and Retirement Study, we found that incarceration and APOE-ε4 genotype (i.e., the chief genetic risk factor for Alzheimer's disease) both constituted substantive risk factors for cognitive impairment in terms of overall risk and earlier onset. The observed effects were mutually independent, however, suggesting that the risk conveyed by incarceration and APOE-ε4 genotype operate across different risk pathways. Our results have implications for the study of criminal-legal contact as a public health risk factor for age-related, neurodegenerative conditions.

Reversible Atmospheric Water Harvesting Using Metal-Organic Frameworks.

The passive capture of clean water from humid air without reliance on bulky equipment and high energy has been a substantial challenge and has attracted significant interest as a potential environmentally friendly alternative to traditional water harvesting methods. Metal-organic frameworks (MOFs) offer a high potential for this application due to their structural versatility which permits scalable, facile modulations of structural and functional elements. Although MOFs are promising materials for water harvesting, little research has been done to address the microstructure-adsorbing characteristics relationship with respect to the dynamic adsorption-desorption process. In this article, we present a parametric study of nine hydrolytically stable MOFs with diverse structures for unraveling fundamental material properties that govern the kinetics of water sequestration in this class of materials as well as investigating overall uptake capacity gravimetrically. The effects of temperature, relative humidity, and powder bed thickness on the adsorption-desorption process are explored for achieving optimal operational parameters. We found that Zr-MOF-808 can produce up to 8.66 LH2O kg-1MOF day-1, an extraordinary finding that outperforms any previously reported values for MOF-based systems. The presented findings help to deepen our understanding and guide the discovery of next-generation water harvesting materials.

UV-cured gel polymer electrolytes with improved stability for advanced aqueous Li-ion batteries.

We report the development of a new class of "water-in-salt" electrolytes based on UV photopolymerized acrylic polymers. Incorporation of "water-in-bisalt" in a polymer matrix reduces water activity, expands the electrochemical stability window to 4.1 V, and dramatically improves cycle life in full cells with lithium titanate anodes compared to liquid water-based electrolytes.

Structural Stability of N-Alkyl-Functionalized Titanium Metal-Organic Frameworks in Aqueous and Humid Environments.

We demonstrate that the highly photoredox active metal-organic framework (MOF) MIL-125-NHCyp exhibits crystalline and porosity stability in humid environments for more than 30 days as well as increased hydrophobicity compared to the unfunctionalized framework. This improved stability, in synergy with its high photocatalytic activity, makes this MOF a very promising candidate for large-scale applications in CO2 photoreduction.