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Tuning the Electronic Properties of Tetravalent Cerium Complexes via Ligand Derivatization
No full textMolecular cerium complexes are of interest due to their remarkable redox and photophysical properties. We have investigated the ligand tunability of the electronic structure and properties of cerium(IV) complexes with functionalized tetradentate N2O2-donor ligands: [CeIV(LtBu)2] (1), [CeIV(LH)2] (2) and [CeIV(LNO2)2] (3), where H2LtBu = bis(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)amine, H2LH = bis(2-hydroxybenzyl)(2-pyridylmethyl)amine and H2LNO2 = bis(2-hydroxy-5-nitrobenzyl)(2-pyridylmethyl)amine. These compounds all exhibit a quasi-reversible one-electron reduction to cerium(III), with the redox potential correlating with the electron donor-acceptor characteristics of the ligand substituents. This correlation is rationalized by energy stabilization of the HOMO, as determined by density functional theory calculations, and is consistent with arene π → Ce 4f* ligand-to-metal charge transfer bands. The L3-edge XANES exhibits minimal variation in Ce 4f occupation for the three compounds, which suggests that the 4f covalent character and composition of the ground-state character do not vary significantly across the series. However, M4,5-edge XAS shows charge transfer satellites that subtly differ in shape and energy, indicating small distinctions in ligand-to-metal charge transfer for the compounds, consistent with small differences in temperature-independent magnetism. The ability to modulate the redox and optical properties of cerium complexes through ligand derivatization highlights the potential for customizable molecular cerium catalysts and photocatalysts
Exploring Physiotherapists' Perspectives of Group Clinical Supervision Effectiveness for Aquatic Physiotherapy Skill Development: A Qualitative Study
No full textBackground and Purpose: Participation in regular clinical supervision is recommended for health professionals to ensure quality of care. Effective clinical supervision of physiotherapists typically consists of a one-to-one model using a combination of reflective and direct approaches to supervision. However, this level of support can be difficult to provide in niche clinical specialities such as aquatic physiotherapy, where one expert clinician is tasked with the supervision of many less experienced clinicians. Group supervision is an alternative model which requires fewer resources, but its effectiveness is unknown. This study aimed to explore physiotherapists' perspectives on the effectiveness of a supervisor-led group supervision model in an aquatic physiotherapy service. Methods: Sixteen physiotherapists at varied career stages who had experienced aquatic physiotherapy group supervision at an inpatient rehabilitation hospital, participated in an interpretive description study using focus groups. Results: Four themes were identified: skill development, specialised practice area, group interactivity, and structure and processes. The positioning theory and interactivity theory informed the data analysis. Discussion: Physiotherapists perceived group clinical supervision to be an effective model for clinical skill development in aquatic physiotherapy. They believed that the model was effective because it afforded them time for reflection in a highly specialised and infrequently practised clinical area. Interactivity between colleagues was viewed as the main strength of group supervision. However, they also felt that skill development would be enhanced if the content of the sessions was structured and group supervision was complemented by direct supervision
The Colors of Legislative Performance: Skin Tone and Effective Lawmaking in Mexico
No full textRecent research from the United States demonstrates lawmakers are marginalized in the legislative process based on ethno-demographic characteristics such as gender, race, and complexion. Is this theoretical explanation generalizable to different country contexts? Examining data from the Mexican Chamber of Deputies, we assess how skin color affects access to leadership and legislative effectiveness—controlling for relevant variables, including sex, education, and experience. Our results confirm that lighter-skinned deputies have greater access to Chamber leadership and are more effective than darker-skinned legislators. However, our results also indicate the lower legislative effectiveness of darker-skinned legislators can be partially explained by a lack of access to leadership. These findings suggest that traditional mechanisms of inclusion (i.e. quotas or reserved seats) are not enough to redress political underrepresentation, as their positive effect on substantive representation is hindered by the obstacles dark-skinned legislators face once in office
TARGET Protein: the effect of augmented administration of enteral protein to critically ill adults on clinical outcomes-statistical analysis plan for a cluster randomized, cross-sectional, double cross-over, clinical trial
No full textBACKGROUND: The TARGET Protein trial will evaluate the effect of greater enteral protein delivery (augmented protein) on clinical outcomes of critically ill adult patients when compared to usual care.
OBJECTIVE: To describe the statistical analysis plan for the TARGET Protein trial.
METHODS: TARGET Protein is a cluster randomized, cross-sectional, double cross-over, open-label, registry-embedded, pragmatic clinical trial conducted across Australia and New Zealand. The trial randomized eight intensive care units (ICU) to receive enteral formula containing either higher dose enteral protein (augmented protein) or usual dose protein in a 1:1 ratio. Each ICU received one trial formula for a 3-month period and then switched to the alternate formulae. This sequence was repeated, for a total trial length of 12 months. The primary outcome is the number of days free of the index hospital and alive at day 90. Secondary outcomes include proportion of patients alive at day 90, survivor-only analysis of days free of the index hospital at day 90, duration of invasive ventilation, ICU and hospital length of stay, incidence of tracheostomy insertion, renal replacement therapy, and discharge destination. The statistical methods and models which will be used to estimate the effects for the primary and secondary outcomes are described. All statistical models will account for the cluster-randomized cross-over design to ensure correct estimation of the 95% confidence intervals. Trial enrolment is complete with 3412 patients enrolled. Data linkage is ongoing.
CONCLUSION: This statistical analysis plan enables transparent reporting of the TARGET Protein trial. It will reduce the risk of potential selective reporting biases.
TRIAL REGISTRATION: Australian New Zealand Clinical Trials Registry (ACTRN12621001484831). Registered on November 1, 2021
Are contemporary antifungal doses sufficient for critically ill patients? Outcomes from an international, multicenter pharmacokinetics study for Screening Antifungal Exposure in Intensive Care Units—the SAFE-ICU study
No full textPURPOSE: Appropriate antifungal therapy is a major determinant of survival in critically ill patients with invasive fungal disease. We sought to describe whether contemporary dosing of antifungals achieves therapeutic exposures in critically ill patients. METHODS: In a prospective, open-label, multicenter pharmacokinetic study, intensive care unit (ICU) patients prescribed azoles, echinocandins, or polyene antifungals for treatment or prophylaxis of invasive fungal disease were enrolled. Blood samples were collected on two occasions, with three samples taken during a single dosing interval on each occasion. Total concentrations were centrally measured using validated chromatographic methods. Pharmacokinetic parameters were estimated using noncompartmental methods. Antifungal dosing adequacy was assessed using predefined PK/PD targets. RESULTS: We included 339 patients from 30 ICUs across 12 countries. Median age 62 (interquartile range [IQR], 51-70) years, median APACHE II score 22 (IQR, 17-28), and 61% males. Antifungal therapy was primarily prescribed for treatment (80.8%). Fluconazole was the most frequently prescribed antifungal (40.7%). The most common indication for treatment was intra-abdominal infection (30.7%). Fungi were identified in 45% of patients, of which only 26% had a minimum inhibitory concentration available. Target attainment was higher for patients receiving prophylaxis (> 80% for most drugs). For patients receiving treatment, low target attainment was noted for voriconazole (57.1%), posaconazole (63.2%), micafungin (64.1%) and amphotericin B (41.7%). CONCLUSION: This study highlights the varying degrees of target attainment across antifungal agents in critically ill patients. While a significant proportion of patients achieved the predefined PK/PD targets, wide variability and subtherapeutic exposures persist. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT03136926, 2017-04-21
Implementing a nurse-enabled, integrated, shared-care model involving specialists and general practitioners in early breast cancer post-treatment follow-up (EMINENT): a single-centre, open-label, phase 2, parallel-group, pilot, randomised, controlled trial
No full textBackground: Current models of post-treatment cancer care rely heavily on hospital-based, medical specialists and do not sufficiently leverage primary care. Many breast cancer survivors face ongoing unmet needs that may benefit from a multidisciplinary, shared-care approach. We aimed to evaluate the feasibility and preliminary effectiveness of implementing nurse-enabled, shared-follow-up care between the acute and primary care setting for early-stage breast cancer. Methods: In this single-centre, open-label, phase II, pilot, randomised, controlled trial, individuals diagnosed with breast cancer (Stage 0–III) were randomised 1:1 to either usual care or intervention, which includes a 1) Specialist Nurse Consultation to co-develop a survivorship care plan (SCP), 2) Pharmacist Consultation, 3) Case Conference with General Practitioner (GP), and 4) shared follow-up care arrangements. Feasibility and effectiveness outcome measures, including health-related quality of life (primary outcome), physical activity and nutrition, patient experience, and financial toxicity were collected at baseline, and at 3-, 6-, and 12-months, with health service utilisation data at 24-months. Bivariate and multivariable, intention-to-treat analyses were conducted. This trial is registered at Anzctr.org.au (ACTRN12619001594112). Findings: From 3rd December 2019 to 13th April 2021, 61 participants were randomised (intervention n = 29; usual care n = 32); mean age 62.9 standard deviation (SD) = 10.9 years. The intervention was feasible with 100% completion rates across all elements of the specialist nurse consultation and GP case conference. Evaluation of the 28 SCPs indicated the top three goals were exercise (n = 23), diet (n = 12) and mental well-being (n = 11). All care goals can be supported by GPs. No differences were observed between groups for health-related quality of life and the other effectiveness outcomes measures listed above at all timepoints (P > 0.05 for all). There were significantly fewer average post-treatment radiation oncology appointments per patient in the intervention group compared to the control group (0.69 versus 1.27, P = 0.013) at 24-months. Number of unplanned hospital presentations at 24-months were low across both intervention (n = 7) and control (n = 4) groups. Interpretation: Nurse-enabled, shared-care arrangements for women with early-stage breast cancer is feasible, and is as safe as specialist-led model of care. It may provide a more sustainable model of care in a longer term. GPs can meet the survivorship care needs identified breast cancer survivors. This trial can inform a large, pragmatic, hybrid effectiveness-implementation trial. Funding: Metro South Health Research Support Scheme Project Grant
Adolescent Hippocampal Development: Impact of Cognitive Training and Maternal Immune Activation in Mice
No full text© 2025 Ulysse Mathieu Claude Corentin ThivisolAdolescence is a vulnerable period of neurodevelopment, coinciding with the onset of neurodevelopmental psychiatric conditions like schizophrenia. However, the neurobiological changes during adolescence that contribute to these conditions are poorly understood. Studies in people with schizophrenia have shown that maturation of the hippocampus is particularly important, and deficits in hippocampal volume and hippocampal-dependent cognition are related to illness progression. However, clinical studies to further understand neurobiological changes are limited to non-invasive and post-mortem measures, while preclinical models are better equipped to study these. This thesis aimed to characterise the maturational trajectories of the adolescent mouse hippocampus in normal development, in response to hippocampal-dependent visuospatial cognitive training, and in a neurodevelopmental prenatal inflammatory insult model relevant for schizophrenia (maternal immune activation, MIA to influenza-A), with a focus on underlying protein changes.
In the first study, hippocampal volume, protein, and visuospatial learning trajectories were mapped in male and female mice across adolescent development, to compare the maturational trajectories of ‘Naive’, cognitively ‘Trained’, and untrained ‘Yoked’ controls. Timepoints correspond with early adolescence (4.5 weeks; W), mid-adolescence (6.5W), late adolescence (8W), and young adulthood (12W and 14W). Hippocampal volume was collected by 9.4 Tesla (T) magnetic resonance imaging (MRI) and hippocampi were excised. Visuospatial learning was assessed in Yoked and Trained mice in the same Paired-Associate Learning (sPAL) task. Western blots assessed relative abundance of proteins relevant to neurodevelopment and synaptic plasticity. Measures were integrated, and their relationships were explored. Hippocampal volume increased with Age and was greater in males, while proteins exhibited a quartic Age trajectory. Cognitive training attenuated hippocampal growth and elevated learning rate and synaptic protein abundance, while Yoked experience reduced mean hippocampal volume and elevated synaptic proteins beyond that of Trained mice. Crucially, the Yoked controls helped delineate the effects of food restriction, task experience, and cognitive training. Integrated analysis illuminated the relationships between brain measures and Age, Group, and Sex, highlighting the role of synaptic regulation.
In the MIA studies, pregnant mice were incubated with either saline control or Hkx31 influenza virus at embryonic day 12.5. Their female and male offspring were raised to 8W or 14W before hippocampal excision. Hippocampi were prepared for mass spectrometry, using 18-plex tandem mass tags. Proteomic analysis revealed that normally sexually dimorphic immunoregulatory proteins were centrally dysregulated in the hippocampi of late adolescent MIA females. Phospho-proteomic analysis discovered further sex-specific changes in late adolescent MIA hippocampi and exclusively female-specific changes in young adult MIA hippocampi. These were primarily postsynaptic proteins involved in neuroplasticity, cytoskeletal structure, cell metabolism, and cell signalling pathways, and suggested that phospho-proteomic dysregulation in MIA females worsens between late adolescence to young adulthood. These studies were the first to examine proteomic changes in the adolescent mouse brain using an influenza-based MIA model, and the first to investigate phospho-proteomic mouse brain changes in adolescent MIA offspring.
Overall, this thesis highlighted the dynamic nature of hippocampal development during adolescence, and the important influence of sex, cognitive experience, and neuroinflammation. Findings yielded important neurobiological insights into neurodevelopmental and psychiatric conditions like schizophrenia and identified promising therapeutic targets
Right Bundle Branch Block After Transvenous Lead Extraction: An Unreported Complication With Potentially Severe Outcomes
No full textINTRODUCTION: Right bundle branch block (RBBB) following cardiac device extraction has not been previously reported but may have catastrophic consequences. METHODS AND RESULTS: We present two cases of young male patients who developed RBBB following the extraction of single chamber TV ICD systems where the coil was adherent close to the superior tricuspid valve annulus. Both patients had a subcutaneous ICD (SICD) implanted but suffered an inappropriate shock due to T-wave oversensing, requiring very early SICD removal for one patient. CONCLUSION: The development of RBBB following the extraction of a TV ICD is a previously unreported complication and may cause significant sensing problems if an SICD is implanted subsequently. Placement of the ICD lead tip in the right ventricular outflow tract or high on the intraventricular septum may predispose to this complication
A national survey of osteopaths’ conceptions of practice in France: structural validity of the Osteo-TAQfr and the tendency toward technical rationality
No full textBACKGROUND: Despite the growing popularity of osteopathy in France, little is known about how French osteopaths conceptualise key aspects of their practice, including skills, knowledge, and decision-making. This study aimed to adapt and validate the Osteopaths' Therapeutic Approaches Questionnaire (Osteo-TAQ) for use in a French osteopathic population (Osteo-TAQfr) and to examine the professional profile and core elements of clinical practice among French osteopaths. The first objective was to establish the psychometric properties of the Osteo-TAQfr within a French osteopathic population. The second aim was to explore French osteopaths' conceptions of practice and their approach to patient care, thereby contributing to a broader understanding of the profession in France and its relevance within the discourse on allied health professions (AHPs). METHODS: A cross-sectional study was conducted to (1) adapt and validate the French version of the Osteopaths' Therapeutic Approaches Questionnaire (Osteo-TAQfr) and (2) explore osteopaths' conceptions of practice in France. The translation and cultural adaptation process was informed by cognitive interviews to ensure linguistic and contextual appropriateness. Exploratory Factor Analysis (EFA) was performed to assess the factor structure in the French osteopathic context and Confirmatory Factor Analysis (CFA) was used to test the validity of previously established constructs-Professional Artistry (PA) and Technical Rationality (TR). Internal consistency was evaluated using McDonald's omega (ω). RESULTS: The survey yielded 1,703 complete responses. Analysis supported a two-factor model with PA andTR subscales, both showing strong reliability estimations (PA ω = 0.882; TR ω = 0.873). Minor theory-informed adjustments improved model fit. A moderate negative correlation was observed between the PA and TR subscales (r=-0.407). Respondents with additional health professions qualifications scored lower on the PA subscale and higher on the TR subscale. CONCLUSIONS: The Osteo-TAQfr is an original tool that assesses conceptions of osteopathic practice in France. Findings reveal a predominance of TR among French osteopaths, characterised by biomedical, technique-driven approaches. These results have significant implications for aligning osteopathic education and practice with contemporary AHP paradigms, including patient-centred care and interdisciplinary collaboration. Further research should explore the transferability of the Osteo-TAQ across other healthcare systems and its potential impact on clinical outcomes and professional development
The role of policy networks in adapting to sea level rise: the case of Victoria, Australia
No full textThis chapter provides a description and evaluation of the process of instigating adaptation to sea level rise through land use planning in Victoria, Australia. Through key actor interviews, and document analysis, this chapter explains how a network of institutions initiated land use planning mechanisms to adapt to sea level rise. This case is significant as it initiated the requirement to plan for sea
level rise within planning instruments, and this has remained a key mechanism for adaptation since. The chapter contributes new evidence and insights that will be beneficial for other locations, by explaining the influence of policy networks on the evolution of adaptation policy through urban planning. This analysis demonstrates
how diverse institutions can advance adaptation to climate change, and that through such networks even institutions without much formal power can be influential in catalysing policy change