ABSTRACT
The electronic structure and local coordination of binary (Mo6T8) and ternary Chevrel Phases (MxMo6T8) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L3-edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides MxMo6T8 (M = Cu, Ni, x = 1-2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo6 clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.
ABSTRACT
In this work, we implement a facile microwave-assisted synthesis method to yield three binary Chevrel-Phase chalcogenides (Mo6X8; X = S, Se, Te) and investigate the effect of increasing chalcogen electronegativity on hydrogen evolution catalytic activity. Density functional theory predictions indicate that increasing chalcogen electronegativity in these materials will yield a favorable electronic structure for proton reduction. This is confirmed experimentally via X-ray absorption spectroscopy as well as traditional electrochemical analysis. We have identified that increasing the electronegativity of X in Mo6X8 increases the hydrogen adsorption strength owing to a favorable shift in the p-band position as well as an increase in the Lewis basicity of the chalcogen, thereby improving hydrogen evolution reaction energetics. We find that Mo6S8 exhibits the highest hydrogen evolution activity of the Mo6X8 series of catalysts, requiring an overpotential of 321 mV to achieve a current density of 10 mA cm-2ECSA, a Tafel slope of 74 mV per decade, and an exchange current density of 6.01 × 10-4 mA cm-2ECSA. Agreement between theory and experiment in this work indicates that the compositionally tunable Chevrel-Phase chalcogenide family is a promising framework for which electronic structure can be predictably modified to improve catalytic small-molecule reduction reactivity.
ABSTRACT
Motivational interviewing (MI) is an empirically supported clinical method to help individuals make behavioral changes to achieve a personal goal. Through a set of specific techniques, MI helps individuals mobilize their own intrinsic values and goals to explore and resolve ambivalence about change. This article examines how MI-informed approaches can be applied to help staff adopt new evidence-based practices in organizational settings. Although the implementation science literature offers strategies for implementing new practices within organizations, leaders of quality improvement initiatives often encounter ambivalence about change among staff. Implementation approaches that require staff to make substantial changes may be facilitated by drawing from MI strategies. These include building a sense of collaboration from the beginning, eliciting "change talk," and addressing any ambivalence encountered. Motivational interviewing techniques may be particularly helpful in working with those in a stage of precontemplation (who have yet to see a reason for change) and those who are contemplating change (who see that a problem exists but are ambivalent about change). This article provides examples of how an MI-informed approach can be applied to help facilitate change in staff within organizations that are implementing quality improvement initiatives. These techniques are illustrated using a representative scenario.
Subject(s)
Cooperative Behavior , Goals , Motivation , Motivational Interviewing , Choice Behavior , Humans , Motivational Interviewing/methods , Organizational InnovationABSTRACT
The virulence-transmission trade-off hypothesis proposed more than 30 years ago is the cornerstone in the study of host-parasite co-evolution. This hypothesis rests on the premise that virulence is an unavoidable and increasing cost because the parasite uses host resources to replicate. This cost associated with replication ultimately results in a deceleration in transmission rate because increasing within-host replication increases host mortality. Empirical tests of predictions of the hypothesis have found mixed support, which cast doubt about its overall generalizability. To quantitatively address this issue, we conducted a meta-analysis of 29 empirical studies, after reviewing over 6000 published papers, addressing the four core relationships between (1) virulence and recovery rate, (2) within-host replication rate and virulence, (3) within-host replication and transmission rate, and (4) virulence and transmission rate. We found strong support for an increasing relationship between replication and virulence, and replication and transmission. Yet, it is still uncertain if these relationships generally decelerate due to high within-study variability. There was insufficient data to quantitatively test the other two core relationships predicted by the theory. Overall, the results suggest that the current empirical evidence provides partial support for the trade-off hypothesis, but more work remains to be done.
Subject(s)
Bacteria/pathogenicity , Disease Transmission, Infectious , Parasites/pathogenicity , Virulence , Viruses/pathogenicity , Animals , Biological Evolution , Host-Pathogen InteractionsABSTRACT
New genetic tools have allowed researchers to compare how the brainstem auditory and vestibular nuclei develop in embryonic chicks and mice.
Subject(s)
Biological Evolution , Ear/physiology , Hearing/physiology , Postural Balance/physiology , Animals , Brain Stem/physiology , Chick Embryo , Cochlear Nucleus/physiology , Gene Expression Regulation, Developmental , Hearing/genetics , Mice , Postural Balance/genetics , Rhombencephalon , Vestibular Nuclei/physiology , Vestibule, Labyrinth/physiologyABSTRACT
Wallenda (WND) is the Drosophila member of a conserved family of dual leucine-zipper kinases (DLK) active in both neuronal regeneration and degeneration. We examined the role of WND over-expression on sensory neuron morphology by driving WND in multiple subtypes of Drosophila photoreceptors. WND overexpression under control of the pan-retinal GAL4 driver GMR causes multiple photoreceptor defects including cell death, rhabdomere degeneration, and axonal sprouting. Individual photoreceptor subtypes were assayed using GAL4 drivers specific for each photoreceptor class. Many R7 and R8 cells exhibit axonal sprouting while some show cell degeneration. Delaying the onset of WND overexpression until 20 days of age showed that older adult R7 cells retain the ability to initiate new axon growth. R1-6 photoreceptor cells degenerate in response to WND expression and exhibit rhodopsin loss and rhabdomere degeneration. RNAi knockdown of the MAPK signaling components Kayak (KAY) and Hemipterous (HEP) attenuates the WND-induced loss of Rh1 rhodopsin. UAS-induced HEP expression is similar to WND expression, causing degeneration in R1-6 photoreceptors and axonal sprouting in R7 photoreceptors. These results demonstrate that WND in adult Drosophila photoreceptor cells acts through MAPK signaling activity with both regenerative and degenerative responses. These photoreceptors provide a tractable experimental model to reveal cellular mechanisms driving contradictory WND signaling responses.
ABSTRACT
In New South Wales, a coordinated extracorporeal membrane oxygenation (ECMO) retrieval program has been in operation since 2007. This study describes the characteristics and outcomes of patients transported by this service. We performed a retrospective observational study and included patients who were transported on ECMO to either of two adult tertiary referral hospitals in Sydney, New South Wales, between February 28, 2007 and February 29, 2016. One hundred and sixty-four ECMO-facilitated transports occurred, involving 160 patients. Of these, 118 patients (74%) were treated with veno-venous (VV) ECMO and 42 patients (26%) were treated with veno-arterial ECMO. The mean (standard deviation, SD) age was 40.4 (15.0) years. Seventy-seven transports (47%) occurred within metropolitan Sydney, 52 (32%) were from rural or regional areas within NSW, 17 (10%) were interstate transfers and 18 (11%) were international transfers. Transfers were by road (58%), fixed wing aircraft (27%) or helicopter (15%). No deaths occurred during transport. The median (interquartile range) duration of ECMO treatment was 8.9 (5.2-15.3) days. One hundred and nineteen patients (74%) were successfully weaned from ECMO and 109 (68%) survived to hospital discharge or transfer. In patients treated with VV ECMO, age, sequential organ failure assessment score, pre-existing immunosuppressive disease, pre-existing diabetes, renal failure requiring dialysis and failed prone positioning prior to ECMO were independently associated with increased mortality. ECMO-facilitated patient transport is feasible, safe, and results in acceptable short-term outcomes. The NSW ECMO Retrieval Service provides specialised support to patients with severe respiratory and cardiovascular illness, who may otherwise be too unstable to undergo inter-hospital transfer to access advanced cardiovascular and critical care services.
Subject(s)
Extracorporeal Membrane Oxygenation/methods , Heart Diseases/therapy , Respiration Disorders/therapy , Transportation of Patients/methods , Adult , Critical Illness/therapy , Extracorporeal Membrane Oxygenation/statistics & numerical data , Female , Humans , Male , Middle Aged , New South Wales , Retrospective Studies , Transportation of Patients/statistics & numerical dataABSTRACT
It is shown that water-in-oil microemulsions (m/e or µE) can produce BaCeO3 (BCO) and LaCoO3 (LCO) precursors. The nanoparticles (NPs) adsorb on AlOOH sols, in much the same way as Turkevich previously immobilised platinum group metal sols. BCO is active in CO and propane oxidation and NO removal under stoichiometric exhaust conditions, but LCO is a better oxidation catalyst. Activity was also seen when Ba,Ce and La,Co are inserted into/segregate at the surface of AlOOH/Al2O3. However, there is only formation of low levels of BCO, CAIO3 (CAO), LCO and LaAIO3 (LAO) perovskites, along with aluminates and separate oxides. The complexing of cations by AlOOH surface-held oxalate ions, albeit with different efficiencies, has also been explored. All three routes yield active catalysts with micro-domains of crystallinity; microemulsions produce the best defined perovskite NPs, but even those from surface segregation have higher turnover numbers than traditional Pt catalysts. Perovskite NPs may open up green chemistry for air pollution control that is consistent with a circular economy.
Subject(s)
Adrenal Gland Neoplasms/complications , Extracorporeal Membrane Oxygenation/methods , Pheochromocytoma/complications , Shock, Cardiogenic/therapy , Adrenal Gland Neoplasms/diagnostic imaging , Adult , Female , Humans , Multiple Organ Failure/etiology , Multiple Organ Failure/therapy , Pheochromocytoma/diagnostic imaging , Severity of Illness Index , Shock, Cardiogenic/etiologyABSTRACT
Cannibalism occurs in a majority of both carnivorous and noncarnivorous animal taxa from invertebrates to mammals. Similarly, infectious parasites are ubiquitous in nature. Thus, interactions between cannibalism and disease occur regularly. While some adaptive benefits of cannibalism are clear, the prevailing view is that the risk of parasite transmission due to cannibalism would increase disease spread and, thus, limit the evolutionary extent of cannibalism throughout the animal kingdom. In contrast, surprisingly little attention has been paid to the other half of the interaction between cannibalism and disease, that is, how cannibalism affects parasites. Here we examine the interaction between cannibalism and parasites and show how advances across independent lines of research suggest that cannibalism can also reduce the prevalence of parasites and, thus, infection risk for cannibals. Cannibalism does this by both directly killing parasites in infected victims and by reducing the number of susceptible hosts, often enhanced by the stage-structured nature of cannibalism and infection. While the well-established view that disease should limit cannibalism has held sway, we present theory and examples from a synthesis of the literature showing how cannibalism may also limit disease and highlight key areas where conceptual and empirical work is needed to resolve this debate.
Subject(s)
Cannibalism , Mammals/parasitology , Animal Diseases , Animals , Biological Evolution , Host-Parasite InteractionsABSTRACT
Peripheral veno-arterial extra-corporeal membrane oxygenation (ECMO) is an artificial circulation that supports patients with severe cardiac and respiratory failure. Differential hypoxia during ECMO support has been reported, and it has been suggested that it is due to the mixing of well-perfused retrograde ECMO flow and poorly-perfused antegrade left ventricle (LV) flow in the aorta. This study aims to quantify the relationship between ECMO support level and location of the mixing zone (MZ) of the ECMO and LV flows. Steady-state and transient computational fluid dynamics (CFD) simulations were performed using a patient-specific geometrical model of the aorta. A range of ECMO support levels (from 5% to 95% of total cardiac output) were evaluated. For ECMO support levels above 70%, the MZ was located in the aortic arch, resulting in perfusion of the arch branches with poorly perfused LV flow. The MZ location was stable over the cardiac cycle for high ECMO flows (>70%), but moved 5cm between systole and diastole for ECMO support level of 60%. This CFD approach has potential to improve individual patient care and ECMO design.
Subject(s)
Aorta/physiopathology , Computer Simulation , Extracorporeal Membrane Oxygenation , Hydrodynamics , Veins/physiopathology , Adult , Cardiac Output , Heart Ventricles/physiopathology , Humans , Male , Models, Biological , Respiratory Insufficiency/physiopathology , Respiratory Insufficiency/therapyABSTRACT
We describe the use of peripheral veno-venous extracorporeal membrane oxygenation (VV ECMO) and high-flow nasal oxygen as procedural support in a patient undergoing debulking of a malignant tumour of the lower airway. Due to the significant risk of complete airway obstruction upon induction of anaesthesia, ECMO was established while the patient was awake, and was maintained without systemic anticoagulation to minimise the risk of intraoperative bleeding. This case illustrates that ECMO support with high-flow nasal oxygen can be considered as part of the algorithm for airway management during surgery for subtotal lower airway obstruction, as it may be the only viable option for maintaining adequate gas exchange.
Subject(s)
Airway Obstruction/surgery , Extracorporeal Membrane Oxygenation/methods , Oxygen/administration & dosage , Tracheal Neoplasms/surgery , Aged , Airway Management/methods , Airway Obstruction/etiology , Cytoreduction Surgical Procedures/methods , Female , Humans , Melanoma/pathology , Melanoma/surgery , Pulmonary Gas Exchange , Tracheal Neoplasms/pathology , Tracheal Neoplasms/secondaryABSTRACT
Herein we detail the cases of three patients transferred on veno-arterial extracorporeal membrane oxygenation (VA ECMO) from a tertiary referral hospital to an ECMO centre. We highlight the benefits of such a transfer and offer this as a model of care for unwell patients likely to require a prolonged period of ECMO support.
Subject(s)
Extracorporeal Membrane Oxygenation/methods , Patient Transfer , Adult , Australia , Female , Humans , Male , Middle Aged , Tertiary Care Centers , Time FactorsABSTRACT
OBJECTIVE: This report describes experiences and outcomes of an online learning collaborative focused on implementation of stagewise treatment. METHODS: Eleven participating programs convened online monthly for a year. Between meetings, program staff created an implementation plan and programs collected performance indicator data, including assessment of staff knowledge of integrated treatment for people with co-occurring disorders, whether a person's current stage of treatment was documented in his or her chart, and whether the treatments were appropriate for the stage of treatment. Descriptive statistics were used to characterize performance indicators and feedback. Wilcoxon matched-pairs signed-rank tests examined changes in performance indicators over time. RESULTS: Program staff generally demonstrated significant improvements in performance indicators over time and rated the distance learning collaborative favorably. CONCLUSIONS: Distance learning collaboratives can be structured to provide opportunities for program staff to interact and learn from one another and to implement and sustain changes.
Subject(s)
Clinical Competence , Cooperative Behavior , Education, Distance/methods , Internet , Psychiatric Rehabilitation/education , Educational Measurement , Evidence-Based Medicine , Humans , Psychiatric Rehabilitation/methodsABSTRACT
BACKGROUND: Transcatheter aortic valve implantation (TAVI) has been developed to treat symptomatic aortic stenosis in patients deemed too high risk for open-heart surgery. To address this complex population, an interdisciplinary heart team approach was proposed. AIM: Present the short- and mid-term outcomes of the first 100 patients in the Royal Prince Alfred Hospital multidisciplinary TAVI programme. METHODS: Single-centre registry. Baseline and procedural data were prospectively recorded. Outcomes were recorded according to Valve Academic Research Consortium - version 2 guidelines. RESULTS: All patients underwent a comprehensive interdisciplinary pre-procedural evaluation. Sixty-eight transfemoral and 32 transapical implantations were performed. Mean age was 82 (±8.9) years old with an average logistic EuroSCORE of 33. Although 13 procedures had major complications, there was no intraprocedural mortality. During the first month, 9% of patients were re-admitted due to heart failure and 13% had a permanent pacemaker implanted. A 3% 30-day and 8% follow-up (mean 17 months) mortalities were recorded. While no significant differences in the rate of complications were found between the first and second half of the experience, all cases of mortality within 30 days (n = 3) occurred in the initial half. Sustained haemodynamic results were obtained with TAVI (immediate mean aortic valve gradient reduction from 47 to 9 mmHg; 1-year echocardiographic gradient 9.9 mmHg, with no moderate or severe aortic regurgitation). CONCLUSION: Excellent results can be achieved with TAVI in very high-risk patients at an Australian institution. A comprehensive evaluation based on a heart team can overcome most of the difficulties imposed by this challenging population.