Strongly facet-dependent activity of iron-doped ß-nickel oxyhydroxide for the oxygen evolution reaction.

Iron (Fe)-doped ß-nickel oxyhydroxide (ß-NiOOH) is a highly active, noble-metal-free electrocatalyst for the oxygen evolution reaction (OER), with the latter being the bottleneck in electrochemical water splitting for sustainable hydrogen production. The mechanisms underlying how the Fe dopant modulates this host material's water electro-oxidation activity are still not entirely clear. Here, we combine hybrid density functional theory (DFT) and Hubbard-corrected DFT to investigate the OER activity of the most thermodynamically favorable (and therefore, expected to be the majority) crystallographic facets of ß-NiOOH, namely (0001) and (101̄0). By considering active sites involving both oxidation and reduction of the transition-metal active center during the redox cycle on these two different facets, we show that six-fold-lattice-coordinated Fe in ß-NiOOH is redox inactive towards both oxidation and reduction while five-fold-lattice-coordinated Fe in ß-NiOOH does exhibit redox activity. However, the determined redox activity of Fe (or lack of it) is not indicative of good (or bad) performance as a dopant on these two facets. Three of the four active sites investigated (oxo and hydroxo sites on (0001) and a hydrated site on (101̄0)) exhibit only a marginal (<0.1 V) decrease or increase in the thermodynamic overpotential upon doping with Fe. Only one of the redox-active sites investigated, the hydroxo site on (101̄0), exhibits a large attenuation in the thermodynamic overpotential upon doping (to ∼0.52 V from 0.86 V), although the doped overpotential is larger than that observed experimentally for Fe-doped NiOOH. Thus, although pure ß-NiOOH facets containing four-, five-, or six-fold lattice-coordinated Ni sites have roughly equal OER activities, yielding similar OER onset potentials (shown in A. Govind Rajan, J. M. P. Martirez and E. A. Carter, J. Am. Chem. Soc., 2020, 142, 3600-3612), only those facets containing four-fold lattice-coordinated Fe (e.g., as shown in J. M. P. Martirez and E. A. Carter, J. Am. Chem. Soc., 2019, 141, 693-705) would be active under analogous conditions for the Fe-doped material. It follows that, while undoped ß-NiOOH demonstrates a roughly facet-independent oxygen evolution activity, the activity of Fe-doped ß-NiOOH strongly depends on the crystallographic facet. Our study further motivates the investigation of strategies for the selective growth of facets with low iron coordination number to enhance the water splitting activity of Fe-doped ß-NiOOH.

Exploring attitudinal barriers to participation in inpatient fall risk assessment using the Theoretical Domains Framework: A survey of providers.

Background and Aims: Lack of provider (physicians and advanced practice providers) participation in fall risk assessment was theorized to be contributing to rising rates of falls with injury at our institution. This project sought to identify if attitudinal barriers to inpatient provider participation in fall risk assessment were similar to those identified in other clinical settings. Methods: Barriers to provider participation in fall risk assessment were identified in the literature. These were mapped to the Theoretical Domains Framework (TDF) domains to assist with interpretation of the data. A 10-item survey using a 5-point Likert scale (strongly agree to strongly disagree) with two open-ended questions was developed using these barriers. The survey was distributed via email to all providers on the Medical Staff in July 2021. Results: The response rate was 9.1% (188/2062). 72.6% (95% confidence interval [CI]: 65.6, 78.5) of providers at our institution did agree that fall risk assessment was within their role and 72% (95% CI: 66.1, 78.5) agreed that assessment can prevent falls. Nearly half felt that they lacked formal training in fall risk assessment (48.1% [95% CI: 41.1, 55.1]) and 52.2% (95% CI: 44.6, 58.6) agreed that other aspects of patient care took priority over falls assessment. These barriers correlated best with the TDF domains of Beliefs about Capabilities and Beliefs about Consequences. Conclusions: Survey results indicate that interventions focused on increasing provider motivation and capability regarding fall risk assessment and helping providers prioritize fall risk assessment are potential targets for future quality improvement projects.

Application of an opioid use disorder cascade of care in a large public health system.

Background: Over the past decade, hospitals and health systems have increasingly adopted interventions to address the needs of patients with substance use disorders. The Opioid Use Disorder (OUD) Cascade of Care provides a framework for organizing and tracking patient health milestones over time and can assist health systems in identifying areas of intervention to maximize the impact of evidence-based services. However, detailed protocols are needed to guide health systems in how to operationalize the OUD Cascade and track outcomes using electronic health records.Objective: In this paper, we describe the process of operationalizing and applying the OUD Cascade in a large, urban, public hospital system.Methods: Through this case example, we describe the technical processes around data mining, as well as the decision-making processes, challenges encountered, lessons learned from compiling preliminary patient data and defining stages and outcome measures for the OUD Cascade of Care, and preliminary dataResults: We identified 33,616 (26.17% female) individuals with an OUD diagnosis. Almost half (48%) engaged with addiction services, while only 10.7% initiated medication-based treatment in an outpatient setting, 6.7% had timely follow-up, and 3.5% were retained for a minimum of 6 months.Conclusion: The current paper serves as a primer for other health systems seeking to implement data-informed approaches to guide more efficient care and improved substance use-related outcomes. An OUD Cascade of Care must be tailored to local systems based on inherent data limitations and services design with an emphasis on early stages wherein drop-off is the greatest.

A human anti-matriptase-2 antibody limits iron overload, α-globin aggregates, and splenomegaly in ß-thalassemic mice.

ABSTRACT: Iron plays a major role in the deterioration of ß-thalassemia. Indeed, the high levels of transferrin saturation and iron delivered to erythroid progenitors are associated with production of α-globin precipitates that negatively affect erythropoiesis. Matriptase-2/TMPRSS6, a membrane-bound serine protease expressed in hepatocytes, negatively modulates hepcidin production and thus is a key target to prevent iron overload in ß-thalassemia. To address safety concerns raised by the suppression of Tmprss6 by antisense oligonucleotides or small interfering RNA, we tested a fully human anti-matriptase-2 antibody, RLYB331, which blocks the protease activity of matriptase-2. When administered weekly to Hbbth3/+ mice, RLYB331 induced hepcidin expression, reduced iron loading, prevented the formation of toxic α-chain/heme aggregates, reduced ros oxygen species formation, and improved reticulocytosis and splenomegaly. To increase the effectiveness of RLYB331 in ß-thalassemia treatment even further, we administered RLYB331 in combination with RAP-536L, a ligand-trapping protein that contains the extracellular domain of activin receptor type IIB and alleviates anemia by promoting differentiation of late-stage erythroid precursors. RAP-536L alone did not prevent iron overload but significantly reduced apoptosis in the erythroid populations of the bone marrow, normalized red blood cell counts, and improved hemoglobin and hematocrit levels. Interestingly, the association of RLYB331 with RAP-536L entirely reversed the ß-thalassemia phenotype in Hbbth3/+ mice and simultaneously corrected iron overload, ineffective erythropoiesis, splenomegaly, and hematological parameters, suggesting that a multifunctional molecule consisting of the fusion of RLYB331 with luspatercept (human version of RAP-536L) would allow administration of a single medication addressing simultaneously the different pathophysiological aspects of ß-thalassemia.

Optimizing delirium care in the era of Age-Friendly Health System.

Delirium is a significant geriatric condition associated with adverse clinical and economic outcomes. The cause of delirium is usually multifactorial, and person-centered multicomponent approaches for proper delirium management are required. In 2017, the John A. Hartford Foundation and the Institute for Healthcare Improvement (IHI) launched a national initiative, Age-Friendly Health System (AFHS), promoting the use of a framework called 4Ms (what matters, medication, mentation, and mobility). The 4Ms framework's primary goal is to provide comprehensive and practical person-centered care for older adults and it aligns with the core concepts of optimal delirium management. In this special article, we demonstrate how a traditional delirium prevention and management model can be assessed from the perspective of AFHS. An example is the crosswalk with the Hospital Elder Life Program (HELP) Core Interventions and the 4MS, which demonstrates alignment in delirium management. We also introduce useful tools to create an AFHS environment in delirium management. Although much has been written about delirium management, there is a need to identify the critical steps in advancing the overall delirium care in the context of the AFHS. In this article, we suggest future directions, including the need for more prospective and comprehensive research to assess the impact of AFHS on delirium care, the need for more innovative and sustainable education platforms, fundamental changes in the healthcare payment system for proper adoption of AFHS in any healthcare setting, and application of AFHS in the community for continuity of care for older adults with delirium.

Does faster weight trajectory lead to improved neurodevelopmental outcomes in ELBW infants with bronchopulmonary dysplasia?

OBJECTIVE: Examine the relationship between weight trajectory and 2-year neurodevelopmental outcomes for extremely low birthweight (ELBW) infants with BPD. STUDY DESIGN: Secondary analysis of infants born from 2010 to 2019. The predictor was BPD severity and the outcome was neurodevelopmental impairment, defined as any Bayley Scales of Infant Development (BSID) III score <70 at 24 months' corrected age. Repeated measures logistic regression was performed. RESULTS: In total, 5042 infants were included. Faster weight trajectory was significantly associated with a decreased probability of having at least one BSID III score <70 for infants with grade 1-2 BPD (p < 0.0001) and an increased probability of at least one BSID III score <70 for infants with grade 3 BPD (p < 0.009). There was no significant association between weight trajectory and BSID III score <70 for infants with grade 0 BPD. CONCLUSION: The association between postnatal weight trajectory and neurodevelopmental outcome in this study differs by BPD severity.

Killer instincts: natural killer cells as multifactorial cancer immunotherapy.

Natural killer (NK) cells integrate heterogeneous signals for activation and inhibition using germline-encoded receptors. These receptors are stochastically co-expressed, and their concurrent engagement and signaling can adjust the sensitivity of individual cells to putative targets. Against cancers, which mutate and evolve under therapeutic and immunologic pressure, the diversity for recognition provided by NK cells may be key to comprehensive cancer control. NK cells are already being trialled as adoptive cell therapy and targets for immunotherapeutic agents. However, strategies to leverage their naturally occurring diversity and agility have not yet been developed. In this review, we discuss the receptors and signaling pathways through which signals for activation or inhibition are generated in NK cells, focusing on their roles in cancer and potential as targets for immunotherapies. Finally, we consider the impacts of receptor co-expression and the potential to engage multiple pathways of NK cell reactivity to maximize the scope and strength of antitumor activities.

Characterizing the Mechanisms of Ca and Mg Carbonate Ion-Pair Formation with Multi-Level Molecular Dynamics/Quantum Mechanics Simulations.

The carbonate minerals of Ca and Mg are abundant throughout the lithosphere and have recently garnered significant research interest as possible long-term carbon sinks in the sequestration of atmospheric carbon dioxide. Nonetheless, an understanding of the atomic-level processes comprising their mineralization remains limited. Here, we characterize and contrast the mechanisms of contact ion-pair formation in aqueous Ca and Mg carbonate systems, which represents the most fundamental step leading to the formation of their mineral solids. Utilizing multilevel embedded correlated wavefunction-based ab initio molecular dynamics/quantum mechanics simulations, we characterize not only the dynamics of these processes but also factors arising from the electronic structure of the involved species, revealing further details of the fundamentally different mechanisms for the interconversion between the contact ion-pairs and solvent-shared ion-pairs of Ca versus Mg carbonate.

A multi-center prospective study of plant-based nutritional support in adult community-based patients at risk of disease-related malnutrition.

Introduction: There is an emerging need for plant-based, vegan options for patients requiring nutritional support. Methods: Twenty-four adults at risk of malnutrition (age: 59 years (SD 18); Sex: 18 female, 6 male; BMI: 19.0 kg/m2 (SD 3.3); multiple diagnoses) requiring plant-based nutritional support participated in a multi-center, prospective study of a (vegan suitable) multi-nutrient, ready-to-drink, oral nutritional supplement (ONS) [1.5 kcal/mL; 300 kcal, 12 g protein/200 mL bottle, mean prescription 275 mL/day (SD 115)] alongside dietary advice for 28 days. Compliance, anthropometry, malnutrition risk, dietary intake, appetite, acceptability, gastrointestinal (GI) tolerance, nutritional goal(s), and safety were assessed. Results: Patients required a plant-based ONS due to personal preference/variety (33%), religious/cultural reasons (28%), veganism/reduce animal-derived consumption (17%), environmental/sustainability reasons (17%), and health reasons (5%). Compliance was 94% (SD 16). High risk of malnutrition ('MUST' score ≥ 2) reduced from 20 to 16 patients (p = 0.046). Body weight (+0.6 kg (SD 1.2), p = 0.02), BMI (+0.2 kg/m2 (SD 0.5), p = 0.03), total mean energy (+387 kcal/day (SD 416), p < 0.0001) and protein intake (+14 g/day (SD 39), p = 0.03), and the number of micronutrients meeting the UK reference nutrient intake (RNI) (7 vs. 14, p = 0.008) significantly increased. Appetite (Simplified Nutritional Appetite Questionnaire (SNAQ) score; p = 0.13) was maintained. Most GI symptoms were stable throughout the study (p > 0.06) with no serious adverse events related. Discussion: This study highlights that plant-based nutrition support using a vegan-suitable plant-based ONS is highly complied with, improving the nutritional outcomes of patients at risk of malnutrition.

Introducing the embedded random phase approximation: H2 dissociative adsorption on Cu(111) as an exemplar.

The random phase approximation (RPA) as a means of treating electron correlation recently has been shown to outperform standard density functional theory (DFT) approximations in a variety of cases. However, the computational cost of the RPA is substantially more than DFT, especially when aiming to study extended surfaces. Properly accounting for sufficient surface ensemble size, Brillouin zone sampling, and vacuum separation of periodic images in standard periodic-planewave-based DFT code raises the cost to achieve converged results. Here, we show that sub-system embedding schemes enable use of the RPA for modeling heterogeneous reactions at reduced computational cost. We explore two different embedded RPA (emb-RPA) approaches, periodic emb-RPA and cluster emb-RPA. We use the (experimentally and theoretically) well-studied H2 dissociative adsorption on Cu(111) as our exemplar, and first perform full periodic RPA calculations as a benchmark. The full RPA results match well the semi-empirical barrier fit to experimental observables and others derived from high-level computations, e.g., from recent embedded n-electron valence second order perturbation theory [Zhao et al., J. Chem. Theory Comput. 16(11), 7078-7088 (2020)] and quantum Monte Carlo [Doblhoff-Dier et al., J. Chem. Theory Comput. 13(7), 3208-3219 (2017)] simulations. Among the two emb-RPA approaches tested, the cluster emb-RPA accurately reproduces the energy profile (maximum error of 50 meV along the reaction pathway) while reducing the computational cost by approximately two orders of magnitude. We therefore expect that the embedded cluster approach will enable wider RPA implementation in heterogeneous catalysis.

Minimizing the impacts of the ammonia economy on the nitrogen cycle and climate.

Ammonia (NH3) is an attractive low-carbon fuel and hydrogen carrier. However, losses and inefficiencies across the value chain could result in reactive nitrogen emissions (NH3, NOx, and N2O), negatively impacting air quality, the environment, human health, and climate. A relatively robust ammonia economy (30 EJ/y) could perturb the global nitrogen cycle by up to 65 Mt/y with a 5% nitrogen loss rate, equivalent to 50% of the current global perturbation caused by fertilizers. Moreover, the emission rate of nitrous oxide (N2O), a potent greenhouse gas and ozone-depleting molecule, determines whether ammonia combustion has a greenhouse footprint comparable to renewable energy sources or higher than coal (100 to 1,400 gCO2e/kWh). The success of the ammonia economy hence hinges on adopting optimal practices and technologies that minimize reactive nitrogen emissions. We discuss how this constraint should be included in the ongoing broad engineering research to reduce environmental concerns and prevent the lock-in of high-leakage practices.

Association between antenatal care facility readiness and provision of care at the client level and facility level in five low- and middle-income countries.

BACKGROUND: Despite growing interest in monitoring improvements in quality of care, data on service quality in low-income and middle-income countries (LMICs) is limited. While health systems researchers have hypothesized the relationship between facility readiness and provision of care, there have been few attempts to quantify this relationship in LMICs. This study assesses the association between facility readiness and provision of care for antenatal care at the client level and facility level. METHODS: To assess the association between provision of care and various facility readiness indices for antenatal care, we used multilevel, multivariable random-effects linear regression models. We tested an inflection point on readiness scores by fitting linear spline models. To compare the coefficients between models, we used a bootstrapping approach and calculated the mean difference between all pairwise comparisons. Analyses were conducted at client and facility levels. RESULTS: Our results showed a small, but significant association between facility readiness and provision of care across countries and most index constructions. The association was most evident in the client-level analyses that had a larger sample size and were adjusted for factors at the facility, health worker, and individual levels. In addition, spline models at a facility readiness score of 50 better fit the data, indicating a plausible threshold effect. CONCLUSIONS: The results of this study suggest that facility readiness is not a proxy for provision of care, but that there is an important association between facility readiness and provision of care. Data on facility readiness is necessary for understanding the foundations of health systems particularly in countries with the lowest levels of service quality. However, a comprehensive view of quality of care should include both facility readiness and provision of care measures.

Single-incision sling operations for urinary incontinence in women.

BACKGROUND: Stress urinary incontinence imposes a significant health and economic burden on individuals and society. Single-incision slings are a minimally-invasive treatment option for stress urinary incontinence. They involve passing a short synthetic device through the anterior vaginal wall to support the mid-urethra. The use of polypropylene mesh in urogynaecology, including mid-urethral slings, is restricted in many countries. This is a review update (previous search date 2012). OBJECTIVES: To assess the effects of single-incision sling operations for treating urinary incontinence in women, and to summarise the principal findings of relevant economic evaluations. SEARCH METHODS: We searched the Cochrane Incontinence Specialised Register, which contains trials identified from: CENTRAL, MEDLINE, MEDLINE In-Process, MEDLINE Epub Ahead of Print, and two trials registers. We handsearched journals, conference proceedings, and reference lists of relevant articles to 20 September 2022. SELECTION CRITERIA: We included randomised or quasi-randomised controlled trials in women with stress (or stress-predominant mixed) urinary incontinence in which at least one, but not all, trial arms included a single-incision sling. DATA COLLECTION AND ANALYSIS: We used standard Cochrane methodological procedures. The primary outcome was subjective cure or improvement of urinary incontinence. MAIN RESULTS: We included 62 studies with a total of 8051 women in this review. We did not identify any studies comparing single-incision slings to no treatment, conservative treatment, colposuspension, or laparoscopic procedures. We assessed most studies as being at low or unclear risk of bias, with five studies at high risk of bias for outcome assessment. Sixteen trials used TVT-Secur, a single-incision sling withdrawn from the market in 2013. The primary analysis in this review excludes trials using TVT-Secur. We report separate analyses for these trials, which did not substantially alter the effect estimates. We identified two cost-effectiveness analyses and one cost-minimisation analysis. Single-incision sling versus autologous fascial sling One study (70 women) compared single-incision slings to autologous fascial slings. It is uncertain if single-incision slings have any effect on risk of dyspareunia (painful sex) or mesh exposure, extrusion or erosion compared with autologous fascial slings. Subjective cure or improvement of urinary incontinence at 12 months, patient-reported pain at 24 months or longer, number of women with urinary retention, quality of life at 12 months and the number of women requiring repeat continence surgery or sling revision were not reported for this comparison. Single-incision sling versus retropubic sling Ten studies compared single-incision slings to retropubic slings. There may be little to no difference between single-incision slings and retropubic slings in subjective cure or improvement of incontinence at 12 months (risk ratio (RR) 0.99, 95% confidence interval (CI) 0.91 to 1.07; 2 trials, 297 women; low-certainty evidence). It is uncertain whether single-incision slings increase the risk of mesh exposure, extrusion or erosion compared with retropubic minimally-invasive slings; the wide confidence interval is consistent with both benefit and harm (RR 1.55, 95% CI 0.24 to 9.82; 3 trials, 267 women; low-certainty evidence). It is uncertain whether single-incision slings lead to fewer women having postoperative urinary retention compared with retropubic slings; the wide confidence interval is consistent with possible benefit and harm (RR 0.47, 95% CI 0.12 to 1.84; 2 trials, 209 women; low-certainty evidence). The effect of single-incision slings on the risk of repeat continence surgery or mesh revision compared with retropubic slings is uncertain (RR 4.19, 95% CI 0.31 to 57.28; 2 trials, 182 women; very low-certainty evidence). One study reported quality of life, but not in a suitable format for analysis. Patient-reported pain at more than 24 months and the number of women with dyspareunia were not reported for this comparison. We downgraded the evidence due to concerns about risks of bias, imprecision and inconsistency. Single-incision sling versus transobturator sling Fifty-one studies compared single-incision slings to transobturator slings. The evidence ranged from high to low certainty. There is no evidence of a difference in subjective cure or improvement of incontinence at 12 months when comparing single-incision slings with transobturator slings (RR 1.00, 95% CI 0.97 to 1.03; 17 trials, 2359 women; high-certainty evidence). Single-incision slings probably have a reduced risk of patient-reported pain at 24 months post-surgery compared with transobturator slings (RR 0.12, 95% CI 0.02 to 0.68; 2 trials, 250 women; moderate-certainty evidence). The effect of single-incision slings on the risk of dyspareunia is uncertain compared with transobturator slings, as the wide confidence interval is consistent with possible benefit and possible harm (RR 0.78, 95% CI 0.41 to 1.48; 8 trials, 810 women; moderate-certainty evidence). There are a similar number of mesh exposures, extrusions or erosions with single-incision slings compared with transobturator slings (RR 0.61, 95% CI 0.39 to 0.96; 16 trials, 2378 women; high-certainty evidence). Single-incision slings probably result in similar or reduced cases of postoperative urinary retention compared with transobturator slings (RR 0.68, 95% CI 0.47 to 0.97; 23 trials, 2891 women; moderate-certainty evidence). Women with single-incision slings may have lower quality of life at 12 months compared to transobturator slings (standardised mean difference (SMD) 0.24, 95% CI 0.09 to 0.39; 8 trials, 698 women; low-certainty evidence). It is unclear whether single-incision slings lead to slightly more women requiring repeat continence surgery or mesh revision compared with transobturator slings (95% CI consistent with possible benefit and harm; RR 1.42, 95% CI 0.94 to 2.16; 13 trials, 1460 women; low-certainty evidence). We downgraded the evidence due to indirectness, imprecision and risks of bias. AUTHORS' CONCLUSIONS: Single-incision sling operations have been extensively researched in randomised controlled trials. They may be as effective as retropubic slings and are as effective as transobturator slings for subjective cure or improvement of stress urinary incontinence at 12 months. It is uncertain if single-incision slings lead to better or worse rates of subjective cure or improvement compared with autologous fascial slings. There are still uncertainties regarding adverse events and longer-term outcomes. Therefore, longer-term data are needed to clarify the safety and long-term effectiveness of single-incision slings compared to other mid-urethral slings.

Application of an Opioid Use Disorder Cascade of Care in a Large Public Health System.

Background: Over the past decade, hospitals and health systems have increasingly adopted interventions to address the needs of patients with substance use disorders. The Opioid Use Disorder (OUD) Cascade of Care provides a framework for organizing and tracking patient health milestones over time, and can assist health systems in identifying areas of intervention to prevent overdose and maximize the impact of evidence-based services for patients with OUD. However, detailed protocols are needed to guide health systems in how to operationalize the OUD Cascade and track outcomes using their systems' electronic medical records (EMR). Objective: In this paper, we describe the process of operationalizing and implementing the OUD Cascade in one large, urban, public hospital system. Methods: Through this case example, we describe the technical processes around data mining, as well as the decision-making processes, challenges encountered, and lessons learned from compiling patient data and defining stages and outcome measures for the OUD Cascade of Care. The current established framework and process will set the stage for subsequent research studies that quantify and evaluate patient progression through each stage of OUD treatment across the health system and identify target areas for quality improvement initiatives to better engage patients in care and improve health outcomes. Results: The current paper can therefore serve as a primer for other health systems seeking to implement a data-informed approach to guide more efficient care and improved substance use-related outcomes. Conclusion: An OUD Cascade of Care must be tailored to local systems based on inherent data limitations and services design.

Probing pH-Dependent Dehydration Dynamics of Mg and Ca Cations in Aqueous Solutions with Multi-Level Quantum Mechanics/Molecular Dynamics Simulations.

The dehydration of aqueous calcium and magnesium cations is the most fundamental process controlling their reactivity in chemical and biological phenomena, such as the formation of ionic solids or passing through ion channels. It holds particular relevance in light of recent advancements in the development of carbon capture techniques that rely on mineralization for long-term carbon storage. Specifically, dehydration of Ca2+ and Mg2+ is a key step in proposed carbon capture processes aiming to exploit the relatively high concentration of dissolved carbon dioxide in seawater via the formation of carbonate minerals from solvated Ca2+ and Mg2+ cations for sequestration and storage. Nevertheless, atomic-scale understanding of the dehydration of aqueous Ca2+ and Mg2+ cations remains limited. Here, we utilize rare event sampling via density functional theory molecular dynamics and embedded wavefunction theory calculations to elucidate the dehydration dynamics of aqueous Ca2+ and Mg2+. Emphasis is placed on the investigation of the effect pH has on the stability of the different coordination environments. Our results reveal significant differences in the dehydration dynamics of the two cations and provide insight into how they may be modulated by pH changes.

Exploring approaches to weighting estimates of facility readiness to provide health services used for estimating input-adjusted effective coverage: a case study using data from Tanzania.

The ideal approach for calculating effective coverage of health services using ecological linking requires accounting for variability in facility readiness to provide health services and patient volume by incorporating adjustments for facility type into estimates of facility readiness and weighting facility readiness estimates by service-specific caseload. The aim of this study is to compare the ideal caseload-weighted facility readiness approach to two alternative approaches: (1) facility-weighted readiness and (2) observation-weighted readiness to assess the suitability of each as a proxy for caseload-weighted facility readiness. We utilised the 2014-2015 Tanzania Service Provision Assessment along with routine health information system data to calculate facility readiness estimates using the three approaches. We then conducted equivalence testing, using the caseload-weighted estimates as the ideal approach and comparing with the facility-weighted estimates and observation-weighted estimates to test for equivalence. Comparing the facility-weighted readiness estimates to the caseload-weighted readiness estimates, we found that 58% of the estimates met the requirements for equivalence. In addition, the facility-weighted readiness estimates consistently underestimated, by a small percentage, facility readiness as compared to the caseload-weighted readiness estimates. Comparing the observation-weighted readiness estimates to the caseload-weighted readiness estimates, we found that 64% of the estimates met the requirements for equivalence. We found that, in this setting, both facility-weighted readiness and observation-weighted readiness may be reasonable proxies for caseload-weighted readiness. However, in a setting with more variability in facility readiness or larger differences in facility readiness between low caseload and high caseload facilities, the observation-weighted approach would be a better option than the facility-weighted approach. While the methods compared showed equivalence, our results suggest that selecting the best method for weighting readiness estimates will require assessing data availability alongside knowledge of the country context.

Solvent Dynamics Are Critical to Understanding Carbon Dioxide Dissolution and Hydration in Water.

Simulations of carbon dioxide (CO2) in water may aid in understanding the impact of its accumulation in aquatic environments and help advance technologies for carbon capture and utilization (via, e.g., mineralization). Quantum mechanical (QM) simulations based on static molecular models with polarizable continuum solvation poorly reproduce the energetics of CO2 hydration to form carbonic acid in water, independent of the level of QM theory employed. Only with density-functional-theory-based molecular dynamics and rare-event sampling, followed by energy corrections based on embedded correlated wavefunction theory (in conjunction with density functional embedding theory), can a close agreement between theory and experiment be achieved. Such multilevel simulations can serve as benchmarks for simpler, less costly models, giving insight into potential errors of the latter. The strong influence of sampling/averaging over dynamical solvent configurations on the energetics stems from the difference in polarity of both the transition state and product (both polar) versus the reactant (nonpolar). When a solute undergoes a change in polarity during reaction, affecting its interaction with the solvent, careful assessment of the energetic contribution of the solvent response to this change is critical. We show that static models (without structural sampling) that incorporate three explicit water molecules can yield far superior results than models with more explicit water molecules because fewer water molecules yield less configurational artifacts. Static models intelligently incorporating both explicit (molecules directly participating in the reaction) and implicit solvation, along with a proper QM theory, e.g., CCSD(T) for closed-shell systems, can close the accuracy gap between static and dynamic models.

Highly Selective Electrochemical Reduction of CO2 into Methane on Nanotwinned Cu.

The electrochemical carbon dioxide reduction reaction (CO2RR) is a promising route to close the carbon cycle by reducing CO2 into valuable fuels and chemicals. Electrocatalysts with high selectivity toward a single product are economically desirable yet challenging to achieve. Herein, we demonstrated a highly (111)-oriented Cu foil electrocatalyst with dense twin boundaries (TB) (tw-Cu) that showed a high Faradaic efficiency of 86.1 ± 5.3% toward CH4 at -1.2 ± 0.02 V vs the reversible hydrogen electrode. Theoretical studies suggested that tw-Cu can significantly lower the reduction barrier for the rate-determining hydrogenation of CO compared to planar Cu(111) under working conditions, which suppressed the competing C-C coupling, leading to the experimentally observed high CH4 selectivity.