Stimuli-responsive anion transport utilising caged hydrazone-based anionophores.

Ion transport across biological membranes, facilitated by naturally occurring ion channels and pumps, plays a crucial role in biological processes. Gating is an important aspect of these systems, whereby transport is regulated by a range of external stimuli such as light, ligands and membrane potential. While synthetic ion transport systems, especially those with gating mechanisms, are rare, they have garnered significant attention due to their potential applications in targeted therapeutics as anticancer agents or to treat channelopathies.

Effect of Ventilator Mode on Ventilator-Free Days in Critically Ill Adults: A Randomized Trial.

Rationale: For critically ill adults receiving invasive mechanical ventilation, the ventilator mode determines how breaths are delivered. Whether the choice of ventilator mode affects outcomes for critically ill patients is unknown. To compare the effects of three common ventilator modes (volume control, pressure control, and adaptive pressure control) on death and duration of mechanical ventilation.

End-of-Life Doulas: A Systematic Integrative Review and Redirection.

Background And Objectives: End-of-life (EOL) doulas (EOLD) are an emerging role providing nonmedical support and advocacy for the dying and their families. Research about EOLD is new and currently highlights a need for more clarity in role definition and application. This review aims to comprehensively analyze existing knowledge regarding EOLD and their role in EOL care.

Evaluating the Efficacy of Time for Living and Caring: An Online Intervention to Support Dementia Caregivers' Use of Respite.

Background And Objectives: Respite, defined as time away from caregiving, is the most requested type of caregiver support. Time for Living and Caring (TLC) is a virtual coaching "app" that helps caregivers schedule and plan their respite time-use. The objectives of this analysis are: (1) to assess the efficacy of the TLC intervention on respite time-use and on caregiver well-being and (2) to identify the key features of the intervention that serve as the likely mechanism of action.

Protocol and Statistical Analysis Plan for the Mode of Ventilation During Critical Illness (MODE) Trial.

Background: For every critically ill adult receiving invasive mechanical ventilation, clinicians must select a mode of ventilation. The mode of ventilation determines whether the ventilator directly controls the tidal volume or the inspiratory pressure. Newer hybrid modes allow clinicians to set a target tidal volume; the ventilator controls and adjusts the inspiratory pressure.

The Impact of Infant Bacille Calmette-Guérin Vaccination on the Immunogenicity of Other Vaccines: A Randomized Exploratory Study.

The effect of the Bacille Calmette-Guérin (BCG) vaccine on the immunogenicity of separately administered serogroup C meningococcal vaccine and other vaccinations was examined in 28 infants randomized to receive BCG at age ≤7 days, at 3 months or after study completion. Immunogenicity of the serogroup C meningococcal vaccine and other routine vaccines might be improved when BCG is administered in early infancy.

Comparison of recruitment methodologies for clinical trials: Results from the time for living and caring (TLC) intervention study.

Background: Recruiting participants for research studies is a critical yet challenging task. Community-engaged recruitment strategies have gained prominence as effective means to engage diverse populations and ensure the representativeness of study samples. This case study aims to investigate the cost and effectiveness of various recruitment methods in enhancing research participation.

Using Digital Inequality Framework to Evaluate a Technology-Delivered Intervention for Caregivers: Age, Education, and Computer Proficiency.

Using "digital inequality" as a conceptual framework, this study evaluates the feasibility and usability of a technology-delivered intervention (an "app") for Alzheimer's and related dementia family caregivers. Time for Living and Caring (TLC) is an on-line intervention that provides virtual coaching and self-administered education and resources. A sample of family caregivers ( = 163) used the tool for 16 weeks, which included completing the Computer Proficiency Questionnaire (CPQ-12) at baseline.

Masked alkynes for synthesis of threaded carbon chains.

Polyynes are chains of sp carbon atoms with alternating single and triple bonds. As they become longer, they evolve towards carbyne, the 1D allotrope of carbon, and they become increasingly unstable. It has been anticipated that long polyynes could be stabilized by supramolecular encapsulation, by threading them through macrocycles to form polyrotaxanes-but, until now, polyyne polyrotaxanes with many threaded macrocycles have been synthetically inaccessible.

Protocol and statistical analysis plan for the Mode of Ventilation During Critical IllnEss (MODE) trial.

Introduction: For every critically ill adult receiving invasive mechanical ventilation, clinicians must select a mode of ventilation. The mode of ventilation determines whether the ventilator directly controls the tidal volume or the inspiratory pressure. Newer hybrid modes allow clinicians to set a target tidal volume, for which the ventilator controls and adjusts the inspiratory pressure.

Memory-like innate response to booster vaccination with MF-59 adjuvanted influenza vaccine in children.

The pediatric population receives the majority of vaccines globally, yet there is a paucity of studies on the transcriptional response induced by immunization in this special population. In this study, we performed a systems-level analysis of immune responses to the trivalent inactivated influenza vaccine adjuvanted with MF-59 in children (15-24 months old) and in young, healthy adults. We analyzed transcriptional responses elicited by vaccination in peripheral blood, as well as cellular and antibody responses following primary and booster vaccinations.

β,β-Directly Linked Porphyrin Rings: Synthesis, Photophysical Properties, and Fullerene Binding.

Cyclic porphyrin oligomers have been studied as models for photosynthetic light-harvesting antenna complexes and as potential receptors for supramolecular chemistry. Here, we report the synthesis of unprecedented β,β-directly linked cyclic zinc porphyrin oligomers, the trimer () and tetramer (), by Yamamoto coupling of a 2,3-dibromoporphyrin precursor. Their three-dimensional structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and single-crystal X-ray diffraction analyses.

Halogen-Bonding Heteroditopic [2]Catenanes for Recognition of Alkali Metal/Halide Ion Pairs.

The first examples of halogen bonding (XB) heteroditopic homo[2]catenanes were prepared by discrete Na template-directed assembly of oligo(ethylene glycol) units derived from XB donor-containing macrocycles and acyclic bis-azide precursors, followed by a Cu -mediated azide-alkyne cycloaddition macrocyclisation reaction. Extensive H NMR spectroscopic studies show the [2]catenane hosts exhibit positive cooperative ion-pair recognition behaviour, wherein XB-mediated halide recognition is enhanced by alkali metal cation pre-complexation. Notably, subtle changes in the catenanes' oligo(ethylene glycol) chain length dramatically alters their ion-binding affinity, stoichiometry, complexation mode, and conformational dynamics.

Variability in X-ray induced effects in [Rh(COD)Cl] with changing experimental parameters.

X-ray characterisation methods have undoubtedly enabled cutting-edge advances in all aspects of materials research. Despite the enormous breadth of information that can be extracted from these techniques, the challenge of radiation-induced sample change and damage remains prevalent. This is largely due to the emergence of modern, high-intensity X-ray source technologies and the growing potential to carry out more complex, longer duration or studies.

Rapid and Scalable Halosulfonylation of Strain-Release Reagents.

Sulfonylated aromatics are commonplace motifs in drugs and agrochemicals. However, methods for the direct synthesis of sulfonylated non-classical arene bioisosteres, which could improve the physicochemical properties of drug and agrochemical candidates, are limited. Here we report a solution to this challenge: a one-pot halosulfonylation of [1.

Synthesis of meta-substituted arene bioisosteres from [3.1.1]propellane.

Small-ring cage hydrocarbons are popular bioisosteres (molecular replacements) for commonly found para-substituted benzene rings in drug design. The utility of these cage structures derives from their superior pharmacokinetic properties compared with their parent aromatics, including improved solubility and reduced susceptibility to metabolism. A prime example is the bicyclo[1.

Beyond Patient-Provider Relationships: Expanding the Roles and Boundaries of Families during Patient End-of-Life.

Role conflict and strain occur when healthcare providers are required to cross boundaries, either voluntarily or involuntarily, to meet the needs of their dying patients. This research is an unobtrusive digital ethnography of a publicly accessible online forum for healthcare providers ( = 242 posts); it explores the boundaries set by families and healthcare providers, and identifies how healthcare providers navigate and which circumstances require them to sometimes cross these professional boundaries. Results indicate that patient-and-family-centered care may not be fully achieved due to the ambiguity in the expected roles played by both families and healthcare providers during patient death and dying.

A Cross-National Examination of Global Gender Inequality and Femicide by Intimate Partners and Family Members.

Using cross-national data, we analyze the effects of economic participation and opportunity, educational attainment, political empowerment, legislating reserved seats for female political candidates, and prevalence of domestic violence victimization on lethal violence against women across 39 nations. These significant factors have been studied individually with little work on their comparative, unique effects on femicide. Our paper makes such a comparison.

Singly and Triply Linked Magnetic Porphyrin Lanthanide Arrays.

The introduction of paramagnetic metal centers into a conjugated π-system is a promising approach toward engineering spintronic materials. Here, we report an investigation of two types of spin-bearing dysprosium(III) and gadolinium(III) porphyrin dimers: singly -linked dimers with twisted conformations and planar edge-fused β,,β-linked tapes. The rare-earth spin centers sit out of the plane of the porphyrin, so that the singly linked dimers are chiral, and their enantiomers can be resolved, whereas the edge-fused tape complexes can be separated into and stereoisomers.

Polyyne [3]Rotaxanes: Synthesis via Dicobalt Carbonyl Complexes and Enhanced Stability.

New strategies for synthesizing polyyne polyrotaxanes are being developed as an approach to stable carbyne "insulated molecular wires". Here we report an active metal template route to polyyne [3]rotaxanes, using dicobalt carbonyl masked alkyne equivalents. We synthesized two [3]rotaxanes, both with the same C polyyne dumbbell component, one with a phenanthroline-based macrocycle and one using a 2,6-pyridyl cycloparaphenylene nanohoop.

"You Feel Very Isolated": Effects of COVID-19 Pandemic on Caregiver Social Connections.

One in five individuals in the United States provides care and support to ill, disabled, and aging family members in the home, leading to feelings of burden, stress, and poor health and well-being. Social support represents an important buffer for family caregivers that allows them to feel less isolated and more positive about their caregiving role. This sequential mixed-methods study aimed to examine the effect of the COVID-19 pandemic on family caregivers' social connections.

Synthesis and Applications of Polysubstituted Bicyclo[1.1.0]butanes.

Bicyclo[1.1.0]butanes (BCBs) are valuable substrates in the "strain release" synthesis of polysubstituted four-membered ring systems, with applications including bioconjugation agents.

Development of isotope-enriched phosphatidylinositol-4- and 5-phosphate cellular mass spectrometry probes.

Synthetic phosphatidylinositol phosphate (PtdIns ) derivatives play a pivotal role in broadening our understanding of PtdIns metabolism. However, the development of such tools is reliant on efficient enantioselective and regioselective synthetic strategies. Here we report the development of a divergent synthetic route applicable to the synthesis of deuterated PtdIns4 and PtdIns5 derivatives.