A lithium-air battery and gas handling system demonstrator.

The lithium-air (Li-air) battery offers one of the highest practical specific energy densities of any battery system at >400 W h kgsystem-1. The practical cell is expected to operate in air, which is flowed into the positive porous electrode where it forms Li2O2 on discharge and is released as O2 on charge. The presence of CO2 and H2O in the gas stream leads to the formation of oxidatively robust side products, Li2CO3 and LiOH, respectively. Thus, a gas handling system is needed to control the flow and remove CO2 and H2O from the gas supply. Here we present the first example of an integrated Li-air battery with in-line gas handling, that allows control over the flow and composition of the gas supplied to a Li-air cell and simultaneous evaluation of the cell and scrubber performance. Our findings reveal that O2 flow can drastically impact the capacity of cells and confirm the need for redox mediators. However, we show that current air-electrode designs translated from fuel cell technology are not suitable for Li-air cells as they result in the need for higher gas flow rates than required theoretically. This puts the scrubber under a high load and increases the requirements for solvent saturation and recapture. Our results clarify the challenges that must be addressed to realise a practical Li-air system and will provide vital insight for future modelling and cell development.

Heterosexual couples' initial role and outcome expectations as predictors of the therapeutic alliance and relationship satisfaction prior to the fourth session.

We sampled routinely collected measures of role and outcome expectations, the expanded therapeutic alliance, and relationship satisfaction completed by 253 heterosexual couples seen by 35 therapists in the Marriage and Family Research Practice Network (Johnson et al., 2017) and investigated these variables as interdependent dyadic processes using the latent congruence model (Cheung, 2009) and the mediated actor-partner interdependence model (Ledermann et al., 2011). Taken together, we found a direct association between a couple's mean role and outcome expectation scores at Session 1 and individual partners' alliance perceptions at Session 3. Further, men rated the alliance more favorably when their outcome expectations were higher and the partners' outcome expectations were less discrepant. In terms of role expectations, both men and women began therapy expecting to be more actively engaged in the process than their partner. Whereas women rated the alliance more favorably when they had high role expectations for their partner as well as themselves, men rated the alliance more favorably when they had high expectations for their female partner's engagement in the therapy. Notably, alliance at Session 3 did not mediate the association between initial expectations and Session 4 relationship satisfaction due to a strong association (r = 0.85) between relationship satisfaction rated prior to Sessions 1 and 4. In other words, although the best predictor of relationship status before the fourth session was how the relationship was perceived before couple therapy began, men's and women's initial role and outcome expectations were important contributors to the early alliance. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Lost in translation: Therapeutic Alliance as a mediator in the relationship between teletherapy and marital satisfaction.

The global impact of the SARS-COV-2 pandemic necessitated a rapid shift to online/teletherapy psychotherapy services. While research suggests the feasibility and efficacy of teletherapy, there is limited investigation into couple teletherapy's impact on satisfaction and therapeutic alliance. This study aimed to address this gap by examining changes in couple satisfaction during tele- and in-person therapy sessions over 12 sessions and exploring whether therapeutic alliance development mediates these changes. Using growth curve modeling in a sample of 416 couples, it found that teletherapy participants initially reported higher couple satisfaction, but improvement in this domain was slower than in-person therapy recipients. The development of the therapeutic alliance mediated this effect via two indirect paths. Implications include the need for focused attention on alliance development in teletherapy and more empirically-informed approaches in couple teletherapy.

Grieving the Loss of a Child and the Use of Online Social Support: An Exploratory Survey Study.

PURPOSE: To describe social media online grief supports, accessing behaviors, psychosocial variables, and feelings of support among individuals grieving the loss of a child aged <18 years. METHOD: This online survey study recruited 26 adults grieving the loss of a child using social media. Dependent variables included feelings of support and frequency of access. Independent variables included sleep disturbance, cognitive function, depression, anxiety, and self-efficacy to manage emotions (SEMA). Data were collected from May to September 2018. RESULTS: Participants' T scores were higher in level of sleep disturbance (mean = 59.4, SD = 6.1), depression (mean = 62.1, SD = 6.1), and anxiety (mean = 62.8, SD = 7.9), and lower in cognitive function (mean = 37.4, SD = 7.3) and SEMA (mean = 39.3, SD = 5.7). SEMA showed a positive correlation with feeling emotionally supported (p = 0.034). Participants who were accessing online grief supports more frequently reported higher levels of emotional support (F = 9.31, p = 0.006). CONCLUSION: Current findings will help guide the design of online grief support interventions for individuals grieving the loss of a child. [Journal of Psychosocial Nursing and Mental Health Services, 62(8), 47-55.].

Voltammetric Evidence of Proton Transport through the Sidewalls of Single-Walled Carbon Nanotubes.

Understanding ion transport in solid materials is crucial in the design of electrochemical devices. Of particular interest in recent years is the study of ion transport across 2-dimensional, atomically thin crystals. In this contribution, we describe the use of a host-guest hybrid redox material based on polyoxometalates (POMs) encapsulated within the internal cavities of single-walled carbon nanotubes (SWNTs) as a model system for exploring ion transport across atomically thin structures. The nanotube sidewall creates a barrier between the redox-active molecules and bulk electrolytes, which can be probed by addressing the redox states of the POMs electrochemically. The electrochemical properties of the {POM}@SWNT system are strongly linked to the nature of the cation in the supporting electrolyte. While acidic electrolytes facilitate rapid, exhaustive, reversible electron transfer and stability during redox cycling, alkaline-salt electrolytes significantly limit redox switching of the encapsulated species. By "plugging" the {POM}@SWNT material with C60-fullerenes, we demonstrate that the primary mode of charge balancing is proton transport through the graphenic lattice of the SWNT sidewalls. Kinetic analysis reveals little kinetic isotope effect on the standard heterogeneous electron transfer rate constant, suggesting that ion transport through the sidewalls is not rate-limiting in our system. The unique capacity of protons and deuterons to travel through graphenic layers unlocks the redox chemistry of nanoconfined redox materials, with significant implications for the use of carbon-coated materials in applications ranging from electrocatalysis to energy storage and beyond.

Prevalence and health outcomes in community-dwelling older adults with comorbid cancer and dementia: a longitudinal analysis.

OBJECTIVES: To examine health outcomes in community-dwelling older adults with: dementia only, cancer only, and comorbid cancer and dementia. METHODS: Longitudinal analysis was conducted using data from 2010 to 2016 waves of the Health and Retirement Study. Health outcomes included mortality, limitations in activities of daily living (ADL) and instrumental activities of daily living (IADL), nursing home utilization, hospital stay, homecare use, self-rated health, and out-of-pocket medical expenditure. Panel regression was used for statistical analysis. RESULTS: The prevalence of comorbid cancer and dementia ranged from 2.56% to 2.97%. Individuals with comorbid cancer and dementia demonstrated a higher likelihood of nursing home utilization and poorer self-rated health but a lower likelihood of hospital stay, homecare use, and out-of-pocket expenditures, compared to the cancer only or dementia only groups. The differences in mortality and ADL and IADL limitations were not statistically significant. CONCLUSION: Comorbid cancer and dementia predicted longer nursing home utilization and poorer self-rated health. The results help guide care planning for individuals with comorbid cancer and dementia.

Emotion dysregulation and couple relationship satisfaction of clinical couples: An actor-partner interdependence model.

Despite the pivotal role that emotion regulation is thought to occupy for individual and relational wellbeing, emotion regulation in couples has been surprisingly understudied. With a clinical sample consisting of 275 couples starting therapy from 2017 to 2022, this study sought to clarify the actor and partner effects of clinical couples' emotion dysregulation on relationship satisfaction. Our results showed that, for partners' emotion dysregulation dimensions, while impulse control difficulties, lack of emotional awareness, and limited emotion regulation strategies were negatively predictive of couple relationship satisfaction, nonacceptance of negative emotions had a positive association with relationship satisfaction. Further, compared with other dimensions of emotion dysregulation, female limited emotion regulation strategies were greater predictors of decreased female relationship satisfaction. We also found significant gender differences in partners' emotion dysregulation dimensions and relationship satisfaction. These results show the significance of addressing emotion dysregulation for both partners at intra- and inter-personal levels simultaneously in couple therapy. Notably, the 275 couples in our sample did not report a clinically distressed relationship, though they attended at least one couple therapy session. Clinical implications and directions for future study are discussed.

Call me maybe? In-person vs. teletherapy outcomes among married couples.

ABSTRACTObjective: The objective of this study was to investigate the effectiveness of teletherapy compared to in-person couple therapy in outcomes such as couple satisfaction, sexual satisfaction, and the therapeutic alliance.Method: Data from 1157 married clients seeking couple therapy were examined. Individual growth curve models were used to analyze changes in the aforementioned outcomes, with teletherapy as a predictor. The study also examined client age and clinic type as moderators.Results: The results indicated that overall, teletherapy is as effective as in-person therapy in improving outcomes. However, there were notable differences in the development of the therapeutic alliance. The alliance improved at twice the rate in in-person therapy as in teletherapy. Clinic type was also found to be a moderator of changes in sexual satisfaction. Clients in group and private practices reported improvements in sexual satisfaction; whereas clients seen in training clinics reported decreases in sexual satisfaction.Conclusion: The study concludes that although teletherapy may be a viable alternative to in-person couple therapy, there are nevertheless differences in the development of the therapeutic alliance that warrant care and further investigation. The setting of the therapy also plays a role in the effectiveness of therapy, although not specific to therapy modality.

Science, Scripture, and Sexuality: The US United Methodist Church at Crossroads.

During the past 50 years, medical and behavioral scientists have made great progress in understanding the variables which influence the development of sexual orientation, identity, and consequent behavior. In most instances, homosexuality is influenced by hormonal, genetic, and immunologic variables during fetal development, and the effects cannot usually be altered without consequence. The recent struggle within The United Methodist Church in the USA reflects the difficulty that society in general has with accepting homosexuality as part of the spectrum of sexuality. Hopefully, understanding the factors influencing sexual orientation will aid in reducing prejudice and eventually bring an end to the pain endured by the LGBTQ community, and the conflict within The United Methodist Church, a prototype of the struggle.

Self-Assembled Surfactant-Polyoxovanadate Soft Materials as Tuneable Vanadium Oxide Cathode Precursors for Lithium-Ion Batteries.

The mixing of [V10 O28 ]6- decavanadate anions with a dicationic gemini surfactant (gem) leads to the spontaneous self-assembly of surfactant-templated nanostructured arrays of decavanadate clusters. Calcination of the material under air yields highly crystalline, sponge-like V2 O5 (gem-V2 O5 ). In contrast, calcination of the amorphous tetrabutylammonium decavanadate allows isolation of a more agglomerated V2 O5 consisting of very small crystallites (TBA-V2 O5 ). Electrochemical analysis of the materials' performance as lithium-ion intercalation electrodes highlights the role of morphology in cathode performance. The large crystallites and long-range microstructure of the gem-V2 O5 cathode deliver higher initial capacity and superior capacity retention than TBA-V2 O5 . The smaller crystallite size and higher surface area of TBA-V2 O5 allow faster lithium insertion and superior rate performance to gem-V2 O5 .

Lithium-Oxygen Batteries and Related Systems: Potential, Status, and Future.

The goal of limiting global warming to 1.5 °C requires a drastic reduction in CO2 emissions across many sectors of the world economy. Batteries are vital to this endeavor, whether used in electric vehicles, to store renewable electricity, or in aviation. Present lithium-ion technologies are preparing the public for this inevitable change, but their maximum theoretical specific capacity presents a limitation. Their high cost is another concern for commercial viability. Metal-air batteries have the highest theoretical energy density of all possible secondary battery technologies and could yield step changes in energy storage, if their practical difficulties could be overcome. The scope of this review is to provide an objective, comprehensive, and authoritative assessment of the intensive work invested in nonaqueous rechargeable metal-air batteries over the past few years, which identified the key problems and guides directions to solve them. We focus primarily on the challenges and outlook for Li-O2 cells but include Na-O2, K-O2, and Mg-O2 cells for comparison. Our review highlights the interdisciplinary nature of this field that involves a combination of materials chemistry, electrochemistry, computation, microscopy, spectroscopy, and surface science. The mechanisms of O2 reduction and evolution are considered in the light of recent findings, along with developments in positive and negative electrodes, electrolytes, electrocatalysis on surfaces and in solution, and the degradative effect of singlet oxygen, which is typically formed in Li-O2 cells.

Molecular redox species for next-generation batteries.

This Tutorial Review describes how the development of dissolved redox-active molecules is beginning to unlock the potential of three of the most promising 'next-generation' battery technologies - lithium-air, lithium-sulfur and redox-flow batteries. Redox-active molecules act as mediators in lithium-air and lithium-sulfur batteries, shuttling charge between electrodes and substrate systems and improving cell performance. In contrast, they act as the charge-storing components in flow batteries. However, in each case the performance of the molecular species is strongly linked to their solubility, electrochemical and chemical stability, and redox potentials. Herein we describe key examples of the use of redox-active molecules in each of these battery technologies and discuss the challenges and opportunities presented by the development and use of redox-active molecules in these applications. We conclude by issuing a "call to arms" to our colleagues within the wider chemical community, whose synthetic, computational, and analytical skills can potentially make invaluable contributions to the development of next-generation batteries and help to unlock of world of potential energy-storage applications.

Electrochemistry of redox-active molecules confined within narrow carbon nanotubes.

Confinement of molecules within nanocontainers can be a powerful tool for controlling the states of guest-molecules, tuning properties of host-nanocontainers and triggering the emergence of synergistic properties within the host-guest systems. Among nanocontainers, single-walled carbon nanotubes - atomically thin cylinders of carbon, with typical diameters below 2 nm and lengths reaching macroscopic dimensions - are ideal hosts for a variety of materials, including inorganic crystals, and organic, inorganic and organometallic molecules. The extremely high aspect ratio of carbon nanotubes is complemented by their functional properties, such as exceptionally high electrical conductivity and thermal, chemical and electrochemical stability, making carbon nanotubes ideal connectors between guest-molecules and macroscopic electrodes. The idea of harnessing nanotubes both as nanocontainers and nanoelectrodes has led to the incorporation of redox-active species entrapped within nanotube cavities where the host-nanotubes may serve as conduits of electrons to/from the guest-molecules, whilst restricting the molecular positions, orientations, and local environment around the redox centres. This review gives a contemporary overview of the status of molecular redox chemistry within ultra-narrow carbon nanotubes (nanotubes with diameters approaching molecular dimensions) highlighting the opportunities, pitfalls, and gaps in understanding of electrochemistry in confinement, including the role of nanotube diameter, size and shape of guest-molecules, type of electrolyte, solvent and other experimental conditions.

Effects of meteorological and land surface modeling uncertainty on errors in winegrape ET calculated with SIMS.

Characterization of model errors is important when applying satellite-driven evapotranspiration (ET) models to water resource management problems. This study examines how uncertainty in meteorological forcing data and land surface modeling propagate through to errors in final ET data calculated using the Satellite Irrigation Management Support (SIMS) model, a computationally efficient ET model driven with satellite surface reflectance values. The model is applied to three instrumented winegrape vineyards over the 2017-2020 time period and the spatial and temporal variation in errors are analyzed. We illustrate how meteorological data inputs can introduce biases that vary in space and at seasonal timescales, but that can persist from year to year. We also observe that errors in SIMS estimates of land surface conductance can have a particularly strong dependence on time of year. Overall, meteorological inputs introduced RMSE of 0.33-0.65 mm/day (7-27%) across sites, while SIMS introduced RMSE of 0.55-0.83 mm/day (19-24%). The relative error contribution from meteorological inputs versus SIMS varied across sites; errors from SIMS were larger at one site, errors from meteorological inputs were larger at a second site, and the error contributions were of equal magnitude at the third site. The similar magnitude of error contributions is significant given that many satellite-driven ET models differ in their approaches to estimating land surface conductance, but often rely on similar or identical meteorological forcing data. The finding is particularly notable given that SIMS makes assumptions about the land surface (no soil evaporation or plant water stress) that do not always hold in practice. The results of this study show that improving SIMS by eliminating these assumptions would result in meteorological inputs dominating the error budget of the model on the whole. This finding underscores the need for further work on characterizing spatial uncertainty in the meteorological forcing of ET. Supplementary Information: The online version contains supplementary material available at 10.1007/s00271-022-00808-9.

Stabilization of Polyoxometalate Charge Carriers via Redox-Driven Nanoconfinement in Single-Walled Carbon Nanotubes.

We describe the preparation of hybrid redox materials based on polyoxomolybdates encapsulated within single-walled carbon nanotubes (SWNTs). Polyoxomolybdates readily oxidize SWNTs under ambient conditions in solution, and here we study their charge-transfer interactions with SWNTs to provide detailed mechanistic insights into the redox-driven encapsulation of these and similar nanoclusters. We are able to correlate the relative redox potentials of the encapsulated clusters with the level of SWNT oxidation in the resultant hybrid materials and use this to show that precise redox tuning is a necessary requirement for successful encapsulation. The host-guest redox materials described here exhibit exceptional electrochemical stability, retaining up to 86 % of their charge capacity over 1000 oxidation/reduction cycles, despite the typical lability and solution-phase electrochemical instability of the polyoxomolybdates we have explored. Our findings illustrate the broad applicability of the redox-driven encapsulation approach to the design and fabrication of tunable, highly conductive, ultra-stable nanoconfined energy materials.

Early Outcomes of Bivalirudin Therapy for Thrombotic Thrombocytopenia and Cerebral Venous Sinus Thrombosis After Ad26.COV2.S Vaccination.

Vaccine-induced thrombotic thrombocytopenia is a newly described disease process in the setting of expanding access to COVID-19 vaccination. The United States Centers for Disease Control and Prevention recommends treatment with an alternative to heparin in patients suspected of having vaccine-induced thrombotic thrombocytopenia. At this time there have been no reported outcomes from the treatment of vaccine-induced thrombotic thrombocytopenia with bivalirudin as a heparin alternative. We describe the early outcomes from the treatment of vaccine-induced thrombotic thrombocytopenia with bivalirudin as a heparin alternative. A 40-year-old Caucasian woman was found to have thrombocytopenia, cerebral venous sinus thrombosis, and pulmonary embolism following vaccination for COVID-19 with Ad26.COV2.S. She exhibited a steady rise in platelet count: 20×109/L at hospital day 0, 115×109/L at discharge on hospital day 6, and 182×109/L on outpatient follow-up on day 9. While the patient exhibited a transient drop in hemoglobin, there was no clinical evidence of bleeding. This patient did not demonstrate any clinical sequelae of thrombosis, and she reported resolution of her headache. Vaccination with Ad26.COV2.S appears to be associated with a small but significant risk for thrombotic thrombocytopenia within 13 days of receipt. The Centers for Disease Control and Prevention guidance to consider an alternative to heparin was not accompanied by specifically recommended alternatives. A single patient treated with bivalirudin for suspected vaccine-induced thrombotic thrombocytopenia subsequently experienced symptom improvement and a rise in platelet count and did not demonstrate any immediate negative outcomes. A provider may consider bivalirudin as an alternative to heparin in patients with suspected vaccine-induced thrombotic thrombocytopenia following Ad26.COV2.S vaccination, pending more definitive research.

Influencing Factors of Inflammatory Bowel Disease-Fatigue: A Path Analysis Model.

BACKGROUND: Fatigue is a common symptom in adults with inflammatory bowel disease (IBD) and is influenced by many physiological, psychological, and situational factors. However, the influencing factors of fatigue associated with IBD have not been evaluated. OBJECTIVE: This study aims to examine factors associated with fatigue during IBD and develop a parsimonious model that describes the influencing factors of fatigue. METHODS: The study was a secondary analysis of cross-sectional data obtained from IBD Partners, an online cohort of adults with the disease, including 12,053 eligible participants. Data were collected using the Patient-Reported Outcomes Measurement Information System short-form scales measuring fatigue, sleep disturbances, pain interference, anxiety, depression, and satisfaction with social roles. Physical activity was measured using a single question. Demographic and clinical variables were collected. Path analysis was computed to identify the direct and indirect effects of situational, physiological, and psychological factors on IBD-fatigue based on the middle range theory of unpleasant symptoms' conceptual framework. RESULTS: Most of the participants were White females. The data best fit a model with situational factors (physical activity and satisfaction with social roles as the mediators). The direct effect of IBD activity, age, sleep disturbances, pain interference, anxiety, and depression on IBD-fatigue was significant. Significant indirect effects were noted on IBD-fatigue from sleep disturbances, pain interference, and depression via physical activity and satisfaction with social roles. DISCUSSION: The study identified two important intervening variables from the tested model. In addition, other symptoms such as sleep, pain, anxiety, and depression are essential and also influence IBD-fatigue.

Developing a theoretically grounded, digital, ecological momentary intervention for parental bereavement care using the ORBIT model-Phase 1.

Current models of bereavement care do not address all of bereaved parents' unique needs. Diverse challenges limit parents' ability to access certain bereavement services. A web-based intervention prototype for bereaved parents was developed. Using convenience and snowball techniques, 14 participants (pediatric providers, software developers, and bereaved parents) were enrolled in a descriptive, cross-sectional feasibility and usability study. While the intervention was generally considered acceptable, three themes were identified to enhance its usability and acceptability: timing; delivery; and revisions. Further intervention development is needed to improve both short- and long-term physical and psychological outcomes for bereaved parents.

Health-Care Professionals Perceived Barriers to Effective Cancer Pain Management in the Home Hospice Setting: Is Dying at Home Really Best?

Hospice health-care professionals (HCP) evaluate and manage cancer pain in patient homes. This study explores HCP's perceptions of barriers that affect pain management for home hospice cancer patients. A convenience sample of 20 experienced hospice HCP were recruited from a regional hospice agency. Data were collected through two focus groups using semistructured interviews and analyzed using a constant comparative approach to generate themes. An unexpected finding revealed patient's religious and cultural beliefs about suffering and family caregiver's beliefs that patients deserve to suffer due to past actions are barriers to pain management in home hospice. Hospice HCP can identify patients at risk for suffering at the end of life. Interventions targeting spiritual suffering and needs are needed. Home hospice HCP have an ethical obligation to address undue suffering through family's withholding of necessary pain medications and should consider alternative placement when home is not suitable for a peaceful death.

A Prospective Study of the Causes of Bruises in Premobile Infants.

OBJECTIVE: This study had 2 objectives. First, to determine the behavior of physicians evaluating premobile infants with bruises. Second, and most importantly, to learn whether infants with unexplained bruising who had been initially evaluated by primary care and emergency department (ED) physicians are as likely to have their bruises attributed to child abuse as those children evaluated by child abuse physicians. METHODS: Primary care, ED, and child abuse pediatricians (CAPs) in King County, Washington, San Mateo, Calif, Albuquerque, NM, La Crosse, Wis, and Torrance, Calif prospectively identified and studied infants younger than 6 months with less than 6 bruises, which were judged by the evaluating clinician to be explained or unexplained after their initial clinical examination. RESULTS: Between March 1, 2010, and March 1, 2017, 63 infants with initially explained and 46 infants with initially unexplained bruises were identified. Infants with unexplained bruises had complete coagulation and abuse evaluations less frequently if they were initially identified by primary care pediatricians or ED providers than by CAPs. After imaging, laboratory, and follow-up, 54.2% (26) of the infants with initially unexplained bruises, including 2 who had been initially diagnosed with accidental injuries, were diagnosed as abused. Three (6.2%) infants had accidental bruising, 6 (12.4%) abuse mimics, 1 (2.5%) self-injury, 1 (2.5%) medical injury, and 11 (22.9%) remained of unknown causation. None had causal coagulation disorders. A total of 65.4% of the 26 abused infants had occult injuries detected by their imaging and laboratory evaluations. Six (23.1%) abused infants were not diagnosed until after they sustained subsequent injuries. Three (11.5%) were recognized abused by police investigation alone. Thirty-eight percent of the abused, bruised infants had a single bruise. Clinicians' estimates of abuse likelihood based on their initial clinical evaluation were inaccurate. Primary care, ED, and child abuse physicians identified abused infants at similar rates. CONCLUSIONS: More than half of premobile infants with initially unexplained bruises were found to be abused. Abuse was as likely for infants identified by primary care and ED providers as for those identified by CAPs. Currently, physicians often do not obtain full abuse evaluations in premobile infants with unexplained bruising. Their initial clinical judgment about abuse likelihood was inadequate. Bruised infants often have clinically occult abusive injuries or will sustain subsequent serious abuse. Bruised infants should have full abuse evaluations and referral for Protective Services and police assessments.