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We compare the electrochemically measured Sand’s time, the time required for the cell potential to diverge when the applied current density exceeds the limiting current, with theoretical predictions for a 0.47 M poly(ethylene oxide) (5 kg mol−1)/LiTFSI electrolyte. The theoretical predictions are made using concentrated solution theory which accounts for both concentration polarization and polymer motion, using independently measured parameters that depend on concentration, c: conductivity (κ), salt diffusion coefficient (D), cationic transference number with respect to the solvent velocity ( t + 0 ), thermodynamic factor 1 + dln f ± dln c , and partial molar volume of the salt ( V ̅ ); f ± is the mean molar activity coefficient of the salt. We find quantitative agreement between experimental data and theoretical predictions. We derive a generalized analytical expression for Sand’s time for electrolytes based on dilute solution theory. This expression correctly predicts the divergence of the Sand’s time at the limiting current, in agreement with experimental data and concentrated solution theory predictions. When the applied current is large compared to the limiting current, the analytical expression approaches the standard expression for Sand’s time used in the literature.

Advances in computational tools for atomic model building are leading to accurate models of large molecular assemblies seen in electron microscopy, often at challenging resolutions of 3-4 Å. We describe new methods in the UCSF ChimeraX molecular modeling package that take advantage of machine-learning structure predictions, provide likelihood-based fitting in maps, and compute per-residue scores to identify modeling errors. Additional model-building tools assist analysis of mutations, post-translational modifications, and interactions with ligands. We present the latest ChimeraX model-building capabilities, including several community-developed extensions. ChimeraX is available free of charge for noncommercial use at https://www.rbvi.ucsf.edu/chimerax. This article is protected by copyright. All rights reserved.

Concentrated solution theory has furthered our understanding of ion transport in electrolytes. This theory can be used to predict salt concentration profiles under an applied current if the transport properties of the electrolyte (conductivity (κ), restricted diffusion coefficient (D), and the cation transference number with respect to the solvent velocity ( t + 0 )), and the thermodynamic factor (T f ) are known. In this work, we provide the first study comparing the predicted salt concentration profiles with measurements based on operando Raman spectroscopy. Concentration polarization is asymmetrical; the increase in salt concentration near the positive electrode is a factor of two greater than the decrease in salt concentration near the negative electrode. We find qualitative agreement between theory and experiment. Further work is needed to resolve the quantitative differences.

Objectives: We explored the perspectives of older veterans in Gerofit, a Department of Veteran Affairs (VA) supervised clinical exercise program, to understand the factors associated with participation and how the program supported personal health goals. Methods: Twenty semistructured interviews were conducted with active and inactive Gerofit participants. We used a hybrid inductive and deductive approach to thematic analysis of transcripts, with the latter informed by the Health Action Process Approach model of behavior change. Results: Active and inactive participants differed in their perspectives about how Gerofit impacted their progress toward meeting personal health goals. Active participants noted program features (e.g., schedule, staffing) as facilitators and suggested greater self-efficacy about program participation compared to inactive participants. Both groups perceived the camaraderie with other veterans as a facilitator. Conclusions: Exercise program features, including camaraderie, are important factors that affect the ability of older veterans to participate in exercise and achieve personal health goals.

The limiting current density of a conventional polymer electrolyte (PS-PEO/LiTFSI) and a single-ion-conducting polymer electrolyte (PSLiTFSI-PEO) was measured using a new approach based on the fitted slopes of the potential obtained from lithiumpolymer-lithium symmetric cells at a constant current density. The results of this method were consistent with those of an alternative framework for identifying the limiting current density taken from the literature. We found the limiting current density of the conventional electrolyte is inversely proportional to electrolyte thickness as expected from theory. The limiting current density of the single-ion-conducting electrolyte was found to be independent of thickness. There are no theories that address the dependence of the limiting current density on thickness for single-ion-conducting electrolytes.

Societal Impact Statement Identifying where introduced animals fit in a food web relative to each other and to endemic species is key for biodiversity conservation planning. Using a multiproxy study of dog feces from eastern Madagascar, we infer that even dogs that spend time in derived grasslands typically eat forest‐derived foods. Regardless of the time that dogs spend in cleared forest, their impacts are likely concentrated on forest‐dwelling prey. If dogs in forests mostly consume threatened endemic animals (and not other introduced animals such as rats), then the exclusion of dogs from protected forests should be a priority. Summary Introduced predators on islands can help control invasive species yet can also contribute to the extirpation and extinction of endemic taxa. The spread of dogs on Madagascar by ~1000 years ago coincided with the introduction of livestock and spread of grazer‐adapted grasslands, and we help evaluate the extent to which modern dogs are part of novel grassland food webs. To infer dog diet, we identified food remains, where possible, and conducted stable isotope ratio analysis for n = 100 modern dog feces collected in derived grassland at varying distances from protected forest edges around Analamazoatra and Andasibe‐Mantadia National Park in eastern Madagascar. Animal remains in feces and the observed range of fecal δ15N values are consistent with dog meals at multiple trophic levels. However, the observed distribution of fecal δ13C values suggest that few dogs in the study area consumed food derived from open C4 grasslands. Existing data suggest that dogs rely primarily on C3 consumers inhabiting forest biomes (forest‐dwelling animals) for their prey, which may include endemics such as tenrecs, Malagasy rodents, and lemurs and introduced rodents such as rats. These findings indicate that dogs are not confined to the anthropogenic niche defined by grazer‐adapted grasslands, but rather use and impact animal food resources associated with protected forests. Higher resolution study of dog diet and mobility can further clarify the potential for dogs to exploit endemic prey, compete with endemic predators, and spread disease across ecotones.

Even though batteries operate at different temperatures depending on their use and state of charge, little work has been done to understand the effects of temperature on the ionic transport properties of the electrolyte. The temperature dependence of these properties is important for predicting how the performance of the battery will change as a function of temperature, along with gaining fundamental insights into the underpinnings of ion transport in these electrolytes. In this study we provide the first investigation of the effect of temperature on ionic conductivity, salt diffusion coefficient, transference number, and the thermodynamic factor of a model polymer electrolyte: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt dissolved in poly(ethylene oxide) (PEO). These properties were measured at 70, 90, and 110 °C. As expected, we see monotonic increases in conductivity and diffusion with increasing temperature. Additionally, monotonic dependencies on temperature were obtained for the transference number and the thermodynamic factor. One presumes that concentration polarization decreases with increasing temperature due to more rapid ion transport. We use concentrated solution theory to predict concentration polarization in lithium-PEO/LiTFSI‑lithium symmetric cells and thereby quantify the effect of temperature on concentration polarization.

Polyacetal electrolytes have been demonstrated as promising alternatives to liquid electrolytes and poly(ethylene oxide) (PEO) for rechargeable lithium-ion batteries; however, the relationship between polymer structure and ion motion is difficult to characterize. Here, we study structure-property trends in ion diffusion with respect to polymer composition for a systematic series of five polyacetals with varying ratios of ethylene oxide (EO) to methylene oxide (MO) units, denoted as P(xEO-yMO), and PEO. We first use 7Li and 19F pulsed-field-gradient NMR spectroscopy to measure cation and anion self-diffusion, respectively, in polymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixtures. At 90 °C, we observe modest changes in Li+ diffusivity across all polymer compositions, while anion (TFSI-) self-diffusion coefficients decrease significantly with increasing MO content. At a given reduced temperature (T - Tg), all polyacetal electrolytes exhibit faster Li+ self-diffusion than PEO. Intriguingly, P(EO-MO) and P(EO-2MO) also show slower TFSI- anion self-diffusion than PEO at a given reduced temperature. Molecular dynamics simulations reveal that shorter distances between acetal oxygen atoms (O-CH2-O) compared to ether oxygens (O-CH2-CH2-O) promote more diverse, often asymmetric, Li+ coordination environments. Raman spectra reveal that anion-rich ion clusters in P(EO-MO) and P(EO-2MO) lead to decreased anion diffusivity, which along with increased cation diffusivity, support the viability of polyacetals as high-performance polymer electrolytes.

DNA methyltransferase 1 (DNMT1) is the enzyme primarily responsible for propagation of the methylation pattern in cells. Mutations in DNMT1 have been linked to the development of adult-onset neurodegenerative disorders; these disease-associated mutations occur in the regulatory replication foci-targeting sequence (RFTS) domain of the protein. The RFTS domain is an endogenous inhibitor of DNMT1 activity that binds to the active site and prevents DNA binding. Here, we examine the impact of the disease-associated mutation A554V on normal RFTS-mediated inhibition of DNMT1. Wild-type and mutant proteins were expressed and purified to homogeneity for biochemical characterization. The mutation increased DNA binding affinity ~8-fold. In addition, the mutant enzyme exhibited increased DNA methylation activity. Circular dichroism (CD) spectroscopy revealed that the mutation does not significantly impact the secondary structure or relative thermal stability of the isolated RFTS domain. However, the mutation resulted in changes in the CD spectrum in the context of the larger protein; a decrease in relative thermal stability was also observed. Collectively, this evidence suggests that A554V disrupts normal RFTS-mediated autoinhibition of DNMT1, resulting in a hyperactive mutant enzyme. While the disease-associated mutation does not significantly impact the isolated RFTS domain, the mutation results in a weakening of the interdomain stabilizing interactions generating a more open, active conformation of DNMT1. Hyperactive mutant DNMT1 could be responsible for the increased DNA methylation observed in affected individuals.

We study the phase behavior of a triblock organic-inorganic hybrid copolymer, poly(polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixture, as a function of temperature. The polymer exhibits a lamellar morphology both in the neat state and in the presence of salt. However, the average grain size increases substantially when the electrolyte is heated above 113 °C. The grain structure of this sample changes reversibly with temperature, that is, smaller grains reappear when the electrolyte is cooled below 113 °C. While annealing block copolymers at high temperatures often leads to an increase in the grain size, this change is generally irreversible. The reason for the reversible change in the grain structure of the POSS-PEO-POSS/LiTFSI electrolyte is discussed. The ionic conductivity of the electrolyte also exhibits reversible changes in this temperature window. Knowledge of the grain structure is crucial for understanding ion transport in nanostructured electrolytes.

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 363–371.

Purpose Two-spirit, lesbian, gay, bisexual, transgender, and queer (2SLGBTQ+) people disproportionally experience health disparities, and hospital pharmacists, given their accessibility and expertise in medication management, are ideally positioned to provide care to this vulnerable population. This study investigated the barriers and facilitators faced by hospital pharmacists when providing care to 2SLGBTQ+ patients, with the goal of informing enhancement of quality care provided to these patients. Methods A mixed-methods triangulation design was utilized, comprising an online survey and qualitative interviews with Canadian hospital pharmacists. The survey used the lens of systemic oppression as a framework and assessed pharmacists' perceptions and knowledge. Survey data were analyzed using descriptive statistics, and interviews were analyzed using thematic analysis. Results A total of 129 individuals participated in the survey, and 15 participants were interviewed. Eleven themes were identified, and findings revealed a complex web of individual, interpersonal, and systemic barriers and facilitators. Pharmacists expressed a lack of proficiency and confidence in discussing 2SLGBTQ+ health topics, further compounded by an apprehension to engage and a fear of causing harm. Pharmacists desired support from their leadership teams and organizations in the form of access to resources, time to engage in training, and workplace environments that encourage discussions about 2SLGBTQ+ health. Conclusion Hospital pharmacists in Canada are willing to provide inclusive care to 2SLGBTQ+ patients but face significant barriers. These findings highlight the need for comprehensive education, supportive workplace cultures, and accessible resources to address health disparities and improve care for 2SLGBTQ+ individuals. [ABSTRACT FROM AUTHOR]

Objective: Children with cleft lip and/or palate (CL/P) are at increased risk for Sleep Disordered Breathing (SDB), particularly Obstructive Sleep Apnea (OSA). At our institution, routine screening for SDB is performed using the Chevrin Pediatric Sleep Questionnaire (PSQ). This analysis is a practice audit looking at the outcomes of screening children with CL/P. Design/Setting/Patients/Participants: A single-center, retrospective analysis was done of all non-syndromic patients with CL/P over the age of 36 months over a 4-year period. Children with known OSA were eliminated from analysis. Main Outcome Measures: Univariate logistic regression was used to assess predictors for SDB (PSQ score > 8) amongst various patient, disease, and treatment characteristics. Outcomes of those screened were tracked. Results: Of the 239 patients in the study cohort, 43 (18%) had positive PSQs. These subjects were more likely to have class III dental occlusion with maxillary retrusion (OR = 2.65, 95% CI: 1.2–5.8, p = 0.02). There were no differences amongst age, type of cleft, Veau classification, BMI, or history of pharyngeal surgery. One third of the group did not complete recommended testing. Twenty-five subjects with positive sleep screening underwent subsequent polysomnography and 21 (84%) had OSA. Conclusion: Routine screening reveals a significant proportion of patients with CL/P with symptoms suggestive of OSA. While several patients did not complete confirmatory testing, those who completed a PSG had a high rate of identification of OSA. After excluding children with known OSA, patients with SDB are also likely to have class III dental occlusion and maxillary retrusion. [ABSTRACT FROM AUTHOR]

The massive end of the gas-phase mass–metallicity relation (MZR) is a sensitive probe of active galactic nuclei (AGN) feedback that is a crucial but highly uncertain component of galaxy evolution models. In this paper, we extend the z ∼ 0.7 MZR by ∼0.5 dex up to log ( M _⋆ / M _⊙ ) ∼ 11.1. We use extremely deep VLT VIMOS spectra from the Large Early Galaxy Astrophysics Census (LEGA-C) survey to measure metallicities for 145 galaxies. The LEGA-C MZR matches the normalization of the z ∼ 0.8 DEEP2 MZR where they overlap, so we combine the two to create an MZR spanning from 9.3 to 11.1 log ( M _⋆ / M _⊙ ). The LEGA-C+DEEP2 MZR at z ∼ 0.7 is offset to slightly lower metallicities (0.05–0.13 dex) than the z ∼ 0 MZR, but it otherwise mirrors the established power-law rise at low/intermediate stellar masses and asymptotic flattening at high stellar masses. We compare the LEGA-C+DEEP2 MZR to the MZR from two cosmological simulations (IllustrisTNG and SIMBA), which predict qualitatively different metallicity trends for high-mass galaxies. This comparison highlights that our extended MZR provides a crucial observational constraint for galaxy evolution models in a mass regime where the MZR is very sensitive to choices about the implementation of AGN feedback.

Historically, cannabis has been valued for its pain-relieving, anti-inflammatory, and calming properties. Ancient civilizations like the Egyptians, Greeks, and Chinese medicines recognized their therapeutic potential. The discovery of the endocannabinoid system, which interacts with cannabis phytoconstituents, has scientifically explained how cannabis affects the human immune system, including the central nervous system (CNS). This review explores the evolving world of cannabis-based treatments, spotlighting its diverse applications. By researching current research and clinical studies, we probe into how cannabinoids like Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD) help to manage conditions ranging from chronic pain, persistent inflammation, cancer, inflammatory bowel disease, and neurological disorders to even viral diseases such as Human Immunodeficiency virus (HIV), SARS-CoV-2. and the emerging monkeypox. The long-term recreational use of cannabis can develop into cannabis use disorder (CUD), and therefore, understanding the factors contributing to the development and maintenance of cannabis addiction, including genetic predisposition, neurobiological mechanisms, and environmental influences, will be timely. Shedding light on the adverse impacts of CUD underscores the importance of early intervention, effective treatment approaches, and public health initiatives to address this complex issue in an evolving landscape of cannabis policies and perceptions.