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Synthesis, characterisation and antibacterial activity of novel Ga(iii) polypyridyl catecholate complexes
No full textGa(III) polypyridyl catecholate complexes of type [Ga(bipy)2(O,O)](NO3) or [Ga(phen)2(O,O)](NO3) respectively were readily synthesised on reaction of Ga(NO3)3 in methanol with 1 equivalent of catecholate ligand
(2,3-DHBA, 3,4-DHBA, 2,3,4-THBA or CafA) and then 2 equivalents of either bipy or phen. The complexes
were characterised in full including by X-ray crystallography, which established that the catecholate
ligands coordinate the Ga(III) centres in a bidentate manner via the two deprotonated hydroxy groups. All
Ga(III) complexes exhibited good in vitro antibacterial activity against the Gram-negative pathogenic bacteria Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa. The complexes were inactive
against the Gram-positive pathogenic bacteria Staphylococcus aureus including against a methicillin resistant Staphylococcus aureus strain (MRSA). [Ga(bipy)2(2,3-DHBA-2H)](NO3)·1.5H2O (1) was shown to be
non toxic in vivo in larvae of Galleria mellonella at doses up to 2000 μg mL−1 and to offer protection at
doses of 100 and 250 µg mL−1 at 48 and 96 h to larvae infected with P. aeruginosa
Whistleblowing Litigation and Legislation in Ireland: Are There Lessons to be Learned?
No full textThe Protected Disclosures Act 2014 is Ireland’s main workplace whistleblowing legislation. It will be amended by the Protected Disclosures (Amendment) Act 2022
on 1 January 2023 on foot of Ireland’s obligation to transpose into national law
Directive 2019/1937/EU of the European Parliament and the Council of 23 October
2019 on the protection of persons who report breaches of Union law. This paper
addresses the question of whether, in amending the 2014 Act, there were lessons
that could have been learnt from the experience in the UK in the operation of its
whistleblowing legislation. In answering this question, the findings of an analysis
of the case law under the 2014 Act between 15 July 2014 and 15 July 2020 are presented and discussed. In conducting the case law analysis, specific issues were assessed, including, procedural issues concerning the forum for the taking of a claim,
costs, fees, processing times, and time limits for presenting penalisation claims and
substantive issues regarding the type of claim and the success rate. The research established that there are deficiencies in the 2014 Act, and in some of its amendments
under the 2022 Act. It also established that there is an inequity in the treatment
under the legislation of ‘employees’ and workers other than employees. The author
concludes that to address these procedural and substantive deficiencies and inequities, Ireland should have gone beyond the minimum standards of the Directive and
looked to the UK for guidance
Socio-ecological determinants of older people’s mental health and well-being during COVID-19: A qualitative analysis within the Irish context
No full textBackground: Evidence indicates that older people with biological and social vulnerabilities are at high risk of short- and long-term consequences related to the COVID-19 pandemic. However, studies have also highlighted that the crisis may present opportunities for personal growth if older individuals are met with appropriate resources and support. Objective: The aim of this study was to explore the perceptions of older people regarding how individual, social, and environmental factors have supported or hindered their well-being and health during COVID-19.Methods: We analyzed data collected between April–May and October–November 2021 from the Well-being, Interventions and Support during Epidemics (WISE) study, a qualitative investigation of community-dwellers based in Ireland and aged 65 years or over. Participants (n = 57) completed written submissions, narrative interviews and/or go-along interviews detailing their experiences during the pandemic. Framework analysis was carried out in NVivo 12 to identify determinants, linkages, and explanations within Bronfenbrenner’s socio-ecological model. Results: The mean age of participants was 74.9 years, 53% were female, 45% lived alone, and 86% lived in areas with high urban influence. Our findings highlight the heterogeneous effect of COVID-19 across diverse older individuals who held distinct concerns, capabilities, and roles in society before and during the pandemic. Multi-scalar contextual characteristics such as individual’s living arrangements, neighborhood social and built environments, as well as social expectations about aging and help seeking, had an influential role in participants’ well-being and available supports. We identified mixed views regarding public health restrictions, but a consensus emerged questioning the suitability of one-size-fits-all approaches based on chronological age. Conclusions: Our results suggest that some negative pandemic consequences could have been avoided by increasing collaboration with older people and with the provision of clearer communications. The interdependencies identified between individual characteristics and socio-ecological factors that influenced participants’ availability of supports and development of adaptive strategies represent areas of opportunity for the development of age-friendly interventions during and beyond public health crises
The Characterisation of a Lactate Biosensor for Real-Time Neurochemical Monitoring of L-Lactate
No full textThe aim of this project was to characterise a first-generation polymer enzyme composite (PEC)
biosensor utilising lactate oxidase for the real-time neurochemical monitoring of lactate. Lactate,
which was originally thought to be nothing but a mere waste product of anaerobic respiration, has
gained recognition as a cell signalling molecule and playing a significant role in long term
potentiation. It has been postulated that lactate may act as a primary energy substrate following
glutamatergic transmission and this idea is foundation of the astrocyte lactate neuron shuttle
hypothesis (ALNSH) which was proposed by Pellerin and Magistretti in 1994. This theory states
that following glutamatergic transmission lactate is exported from astrocytes to neurons where it
is used for oxidative phosphorylation. Lactate has also shown promise as a biomarker for sleep
and lactate dysregulation in the brain has been shown to be a feature of schizophrenia and autism
spectrum disorder. Electrochemical PEC biosensors used for the monitoring of other neuro
metabolites such as glucose and pyruvate have been previously developed and characterised by
members of the Lowry research group. A PEC lactate biosensor has also been previously
developed, so the core components (cross-linking/stabilising agents and enzyme), layering
strategies and drying times have been optimised to provide a sensitive sensor that now required to
be characterised in vitro and in vivo. Tests included verifying the sensors signal over the range of
temperatures and pHs it would encounter. As the brain is a harsh environment with low [O2]
compared to benchtop conditions, oxygen dependence tests were performed to ensure the signal
given on benchtop conditions was representative of what will be seen at vivo oxygen
concentrations. Biocompatibility tests were performed to ensure minimal signal loss from
electrode poisons, surface modifying agents and surfactants. Finally, interference testing was done
to ensure minimal signal contribution from electroactive reducing agents, electrocatalysts, and
endogenous electroactive interferents e.g. ascorbic acid. In summary, it showed appropriate
sensitivity (0.242 ± 0.014 nA/µM) and excellent stability/biocompatibility with no significant
decrease in sensitivity following ex-vivo storage in rodent brain tissue (14 days) or 28 days in dry
storage. Interference from endogenous electroactive interferents was minimal with extracellular
concentrations typically being ~3% of the 350 µM L-lactate response. Changes in molecular
oxygen (the natural enzyme mediator) over the normal range found in brain tissue (40-80 µM) had
minimal effect on the L-lactate signal for concentrations of 350 and 500 µM (KMO2 of 39.4 ± 17.5
µM and 40.4 ± 16.1 µM respectively). Alongside this a low µM limited of detection (0.153 ±
iv
0.098), was calculated with a slower than expected response time of ca. 18 seconds, combined
with no effect of pH and temperature changes over physiologically relevant ranges (7.2-7,6 and
34-40 °C respectively), collectively suggest this composite biosensor has the ability to reliably
monitor L-lactate in the brain. The sensor was then implanted into the striatum of freely moving
rats where it demonstrated stable recording over several weeks and reliable detection of
physiological changes in L-lactate. The sensors’ ability to provide a reliable signal with changes
in [O2] was proven, following this changes in L-lactate were monitored in response to neuronal
activation (tail-pinch). Future work will focus on pharmacological interventions and the effect
these have on extracellular fluid levels of lactate, which will hopefully aide in our understanding
of how these interventions affect brain metabolism
Notes from the Trenches: Reflections from Recent PhD Graduates on Navigating the Academy
No full textPhD planning graduates face an increasingly competitive academic job market. In this commentary, seven recent graduates provide qualitative descriptions of the complicated and ever-changing expectations graduates face. We situate this within a larger reflection on the neoliberal academy that promotes a culture of competitiveness over care and production over purpose. We emphasize how this system is seemingly antithetical to the transformative planning work needed to address the most pressing planning issues of our time and provide suggestions for meeting shifting expectations, evolving training and support needs, and opportunities for a more compassionate tenure-track market. Our commentary has implications for doctoral pedagogy, the tenure-track market, and the academy
The revival of the drylands: re-learning resilience to climate change from pastoral livelihoods in East Africa
No full textDrylands, seen from the outside world, fall in the imaginary of the remote, the deserted, the unproductive; a powerful imaginary rooted in romantic narratives, as well as in political and economic interests. In this article, we review different waves of rural politics and development in the East African drylands, with a particular focus on Kenya's arid and semi-arid lands, in the context of climate change. We question the re-awakening of international and national attention paid to the drylands under the all-embracing framework of ‘resilience building’. Unfortunately, tensions between climate change policies and local knowledge and practices remain. We show how such renewed attention retains old myths about drylands and leaves little space to the agency of pastoral communities that live in these territories, and what are the implications of mislead development efforts. On the contrary, we suggest learning from pastoral practices to unravel theoretical and policy alternatives
Climate Change Impacts on Irish River Flows: High Resolution Scenarios and Comparison with CORDEX and CMIP6 Ensembles
No full textClimate change is likely to impact water quality, resource availability and riverine ecosystems. While large ensembles are available to assess future impacts (e.g., the Coupled
Model Intercomparison Projects (CMIP) and/or CORDEX) many countries have developed their own high-resolution ensembles. This poses a selection problem with robust adaptation dependent on plausible ranges of change being adequately quantified. Therefore,
it is important to compare projected changes from available ensembles. Here we assess
future climate change impacts for 26 Irish catchments. Using a high-resolution national
ensemble of climate models projected impacts in mean, low and high flows are assessed
and uncertainties in future projections related to catchment size. We then compare future
impacts from CORDEX and CMIP6 ensembles for a subset of catchments. Results suggest increases in winter flows (-3.29 to 59.63%), with wide ranges of change simulated
for summer (-59.18 to 31.23%), low (-49.30 to 22.37%) and food (-19.31 to 116.34%)
flows across catchments under RCP8.5 by the 2080s. These changes would challenge
water management without adaptation. Smaller catchments tend to show the most extreme
impacts and widest ranges of change in summer, low and food flow changes. Both the
ensemble mean and range of changes from the national ensemble were more modest and
narrower than the CMIP6 and CORDEX ensembles, especially for summer mean and
low flows, highlighting the importance of evaluating impacts across ensembles to ensure
adaptation decisions are informed by plausible ranges of change
Climate change impacts on spatial and seasonal meteorological drought characteristics for the island of Ireland
No full textUnderstanding how climate change is likely to impact on meteorological droughts is key to informing adaptation planning. For Ireland, little research has examined how droughts are likely to change in future. Here we examine changes in the monthly climate water balance, aridity index and changes in magnitude, frequency and duration of droughts using standardized drought indices for the island of Ireland derived from bias-adjusted CORDEX simulations for the 2080s(2070–2099), forced with a high (RCP8.5) and moderate (RCP4.5) emissions path-way. Findings highlight that increases in potential evapotranspiration, driven by increasing temperature, together with changing seasonal rainfall patterns increase aridity in summer with water deficits extending into spring months, especially in the east and midlands by the end of the century. Increases in drought frequency and magnitude are also evident, with greatest increases for RCP8.5. Critically, increases are considerably greater for the standardized precipitation evapotranspiration index (SPEI) than for the standardized precipitation index (SPI), emphasizing the importance of using metrics that capture potential evapotranspiration in monitoring and assessing future drought risk. Summer and spring show the greatest increase in drought magnitude and frequency, most marked in the east of the island. By contrast, multi seasonal droughts, assessed using 6-month accumulation periods show more modest changes in magnitude and duration. The resultant impacts of climate change on drought for Ireland would require considerable adaptation given the vulnerabilities exposed by the 2018 drough
Sleep in Childhood Attention Deficit Hyperactivity Disorder
No full textBackground
Sleep impairments frequently co-occur in children with Attention Deficit Hyperactivity Disorder (ADHD), and the nature of their relationship is bidirectional. Sleep problems in this population manifest as difficulties falling asleep, maintaining sleep and in poorer sleep quality, greater daytime sleepiness, altered sleep duration and increased limb movement in sleep. These concerns affect the quality of life, academic performance, cognitive functions, behavioural and family health of the child, negatively impacting their functional outcomes. Early identification and management of sleep problems in this population therefore has deep-rooted clinical utility. In this thesis we aimed to comprehensively delineate the nature of sleep problems in children with ADHD, explore the possible ADHD related cognitive/behavioural facets and environmental factors that might be influencing the child’s sleep and translate our understanding to the design of ADHD-specific sleep assessment tool for clinical utility.
Methods and Results
Chapter 2 reports the systematic review of studies investigating sleep in children between the age of 5-13 years who are diagnosed with ADHD. 148 empirical studies published between 2009-2019 were reviewed and a narrative synthesis was presented categorising studies into five sections. These included studies exploring the nature of these difficulties (subjective reports, sleep macrostructure and microstructure); studies exploring circadian rhythm patterns in this population, consequences of sleep problems, non-pharmacological interventions affecting sleep and ADHD symptoms, and pharmacological interventions affecting sleep in this population. We found that sleep disturbances may worsen behavioral outcomes; moreover, sleep interventions may improve ADHD symptoms, and pharmacotherapy for ADHD may
impact sleep. Gaps in research focussed on the need for using mixed methodologies utilizing objective and subjective reports of sleep, designing well powered studies that define the role of sleep in ADHD clinical picture and facilitate assessment and management of sleep problems.
Chapter 3 qualitatively investigated the nature of sleep problems and sleep related behaviours in children with ADHD. 26 parents of children diagnosed with ADHD aged between 6-12 years were interviewed about their child’s sleep. Thematic analysis of the interviews generated three broad themes which revolved around facets of children’s sleep difficulties as perceived by parents, the perceived impacts of these difficulties, and steps taken by parents to improve their child’s sleep. Parents expressed that sleep problems can be a significant disruptor for their children’s functioning and the wider household. Parents reported using need-based individualised behavioural and sleep hygiene approaches to counter their child’s sleep problems.
Chapter 4 examined the associations of parent-rated sleep problems and sleep timings of pre-adolescent ADHD children with parental insomnia symptoms, ADHD (screener based) features and dysfunctional attitudes and beliefs about sleep (in 120 parent-child pairs). 82% of children exceeded the threshold for a paediatric sleep disorder, and parental insomnia, ADHD symptoms and dysfunctional beliefs about sleep were associated with childrens’s sleep problem scores, and with the subfactors of sleep anxiety and parasomnias. Sleep was poorer for children whose parents were both insomnia probable and had ADHD consistent features, thereby underlying the significant double impact of both on the child.
In Chapter 5, a thirty-five-item parent rated sleep problems questionnaire for children with ADHD was developed. This questionnaire, called Childhood ADHD Sleep Scale (CASS), included 5 domains: Bedtime, Behaviours in Sleep, Sleep Quality, Daytime Functions and Impacts on Family, where the respondent has to choose one out of five options for a sleep
problem statement (‘strongly agree’, ‘somewhat agree’, ‘neither agree or disagree’, ‘somewhat disagree’, and ‘strongly disagree’). CASS showed acceptable test-retest reliability and good internal consistency. Exploratory factor analysis of the CASS generated the 4-factor reduced CASS including sleep problems and impacts, executive and sensory regulation, daytime functions, and parasomnias. The reduced CASS demonstrated good test-retest reliability and internal consistency. Both unreduced CASS and reduced CASS were compared with scores from Child Sleep Habits Questionnaire (CSHQ) and Brown Executive Functions and Attention Scales (Brown -EFA). Differences in the trends of associations were discussed, to understand the utility of an ADHD specific sleep assessment questionnaire.
In Chapter 6, we used an emotional Stroop test to assess the presence of sleep related attentional bias in 155 young adults and examined whether their Stroop test performance and sleep bias scores would associate with their ADHD screener-based symptom scores. Sleep quality scores, insomnia probability scores and social jetlag and chronotype. ADHD consistency scores, and insomnia probability scores were not found to be associated with sleep attentional bias scores. Sleep attentional bias also did not associate with chronotype or social jetlag, but it was found that habitual use of alarm clocks on workfree days did associate with greater sleep attentional bias, indicating that curtailed sleep due to functional demands on these days might increase attention towards sleep related stimulus.
Conclusion
This thesis highlighted how sleep functioning manifests in the clinical picture of childhood ADHD. The bidirectional relationship between the two entities were explored through varied methodological approaches to draw associations between the child’s environment, their own neurodevelopmental diversity and the accompanying sleep features that define their ADHD specific sleep functioning. We aimed at creating a framework within
which sleep problems in ADHD can be understood and utilized for clinical utility, both in terms of assessment and management of these concerns. We also found that social demands can enhance cognitive processing of sleep related stimulus in older cohorts with or without ADHD features
Promoting Collections using Digital Engagement at MU Library (Poster & Booklet)
No full textDigital booklet for the Poster Presentation at the CONUL Conference, 24-25th May 2023, Cork