NUI Maynooth Eprint Archive
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Electrocatalytic Studies of Coral-Shaped Samarium Stannate Nanoparticles for Selective Detection of Azathioprine in Biological Samples
An electrochemical sensor was developed based on the pyrochlore-type binary metal oxide samarium stannate nanoparticles (Sm2Sn2O7 NPs). The Sm2Sn2O7 NPs were prepared using the co-precipitation technique, and they were subjected to physiochemical characterizations such as X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The morphological and elemental information was interpreted by field-emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) analysis. The electrocatalytic sensing of the pharmaceutical drug azathioprine (AZN) was exhibited using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) over the Sm2Sn2O7/GCE (GCE - glassy carbon electrode). The Sm2Sn2O7/GCE had high electrocatalytic behavior for AZN determination with a limit of detection of 4 nM and superior sensitivity of 0.27 μA μM–1 cm–2, and it has a linear range from 0.01 to 948 μM. Furthermore, the Sm2Sn2O7/GCE exhibited excellent selectivity, long-term storage stability, good repeatability, and reproducibility for AZN detection. Additionally, the Sm2Sn2O7/GCE sensor possessed considerable importance for the sensing of AZN in biological fluids for practical applications. We believe that this pyrochlore-based Sm2Sn2O7 NP electrocatalyst can act as a prospective electrode material for the electrochemical determination of AZN in clinical biological applications
Magnetic hydroxyapatite nanocomposites: The advances from synthesis to biomedical applications
Nanoscale materials continue to amaze researchers due to their fascinating versatile properties. One such inspiring development in nanomaterials is the design of the nanocomposite materials for multifunctional purposes
from energy storage to biomedical applications. Magnetic hydroxyapatite [MHAp] nanoparticles have achieved
considerable attention during the last two decades and possess exceptional prospects in the field of
nanomedicine with improved multi-therapeutic approaches. The progress from controlled fabrication to advanced applications of MHAp nanocomposites is still in its infancy and few efforts have been devoted to this
cause. The hybrid structure of MHAp is anticipated to be an auspicious platform for biomedical applications particularly in cancer theranostics because of good stability and biocompatibility. In this review, recent exciting features in the development of MHAp nanocomposite and promising applications in controlled drug/gene delivery
and magnetic hyperthermia treatment, tissue engineering and bone regeneration, antimicrobial activity, heavy
metals and toxic dyes removal, fire retardant behaviour, biosensors and the development of contrast agents for
magnetic resonance imaging are highlighted and explained in detail. In addition, this study provides a comprehensive assessment of the synthesis of MHAp nanocomposites by various preparation methods, the influence
of reaction parameters on the morphology and structure-property relationships based on recent studies. Finally,
novel perceptions are examined regarding the ability of MHAp nanoparticles to improve hybrid nanocarriers
with homogeneous structure to enhance multifunctional biomedical applications
Investigating Structural Property Relationships to Enable Repurposing of Pharmaceuticals as Zinc Ionophores
The importance of zinc in biology has gained greater recognition in recent years due to its essential contributions to the function of many endogenous enzymes. Disruption of zinc homeostasis may be useful in treating pathological conditions, such as Alzheimer’s, and for antiviral purposes. Despite the growth of knowledge and increased interest in zinc, little is known about the structureand function of zinc ionophores. In this study we analyse the Cambridge Structural Database and
solution complexation studies found in the literature to identify key functional groups which may confer zinc ionophorism. Pharmaceuticals, nutraceuticals and amino acids with these functionalities were selected to enable us to explore the translatability of ionophoric activity from in vitro assays to cellular systems. We find that although certain species may complex to zinc in the solid and solution states, and may carry ions across simple membrane systems, this does not necessarily translate into
ionophoric activity. We propose that the CSD can help refine key functionalities but that ionophoric activity must be confirmed in cellular system
Who's to blame? The role of power and attributions in susceptibility to match-fixing
Objective
Official reports and anecdotal evidence suggest that people with power frequently put pressure on athletes to fix a match. Therefore, it is assumed that athletes may attribute their involvement to this pressure. The present study was designed to investigate the role that power, attributions and moral emotions may play in the decision to fix a match.
Method
Team and individual sport athletes (N = 427) competing in five European countries participated in a quasi-experimental vignette design. Participants completed eight vignettes manipulating power, source of attributions and stability of attributions. Match-fixing susceptibility and five discrete anticipated moral emotions (guilt, shame, pride, indifference, anger) were measured.
Results
The results of the analyses demonstrated that athletes are perceived to be most susceptible to match-fixing when the reason is related to a stable attribute of the individual (e.g., enjoying gambling, having a betting problem). However, participants reported also being susceptible to match-fixing when power is high. Anticipated emotions negatively predicted match-fixing susceptibility and mediated the effect of attributions and power on match-fixing susceptibility.
Conclusion
The findings provide information on the interplay between attributions, power and anticipated emotions in predicting match-fixing susceptibility, and the determinants of match-fixing susceptibility. This will be of benefit to policy makers, sporting organizations and researchers in developing policies and interventions to protect athletes from being vulnerable to match-fixing requests
Communicating Uncertainty in Climate Information for China: Recommendations and Lessons Learned for Climate Services
Uncertainty is an inherent characteristic of climate forecasts and projections. While there is an expanding body of international research on identifying what climate information users need to know about uncertainty, and how this should be communicated, very little of this has been conducted in a Chinese cultural context. In this paper, we report on the findings of interviews with climate experts (n = 28) and (potential) users of climate information in China (n = 18) at seasonal and multidecadal timescales, with the objective of addressing the following research questions: (1) What information about uncertainty in climate forecasts and projections is currently provided to users in China? (2) What do climate experts believe that users need to know about uncertainty? (3) What information about uncertainty would (potential) users like to receive? (4) What challenges do providers and users perceive with respect to the communication of uncertainty? We find that while seasonal forecasts are predominantly presented deterministically, current and potential users are aware that there is uncertainty associated with them. Climate experts highlight the probabilistic nature of forecasts and the conditional nature of forecast quality, as areas for communication development. Interviews with (potential) users indicate that (1) preferences for deterministic information are not unanimous; (2) probabilities associated with conditions being above/below normal may only be considered useful for decision-making if they are > 60%; and (3) forecasts that provide tailored statements on probability of user-relevant thresholds are preferred. At multidecadal timescales, we observe lower engagement with projections, and less evidence of interaction between providers and recipients, suggesting that development of climate services at multidecadal timescales will need to first highlight the added value of these. We present key recommendations for communicating uncertainty in seasonal forecasts and explore the potential value of multidecadal projections
Brave enough to fight? Masculinity, migration and the Irish revolution
This article focuses on the nationalist side in revolutionary Ireland (1912–23), examining concepts of bravery, heroic masculinity, fighting for principles and country, all of which have important impacts on understandings of masculinities during the time period (and
indeed before and beyond it). Contemporary nationalist rhetoric emphasised the need to rally all men for an armed struggle: such language paid no heed to the economic realities of many families in Ireland that still needed adult children to migrate. Historians of this
period have done much to uncover the contributions of various groups, but they have rarely examined the gendered ideologies surrounding men in this period, nor have they taken on board the insights from international histories of violence, war and revolution that have interrogated militaristic forms of masculinity in other countries
Interpreting change through legal culture: the case of the Irish exclusionary rule
The changes to the Irish exclusionary rule introduced by the judgment in People (DPP) v JC mark an
important watershed in the Irish law of evidence and Irish legal culture more generally. The case relaxed
the exclusionary rule established in People (DPP) v Kenny, one of the strictest in the common law world,
by creating an exception based on ‘inadvertence’. This paper examines the decision through the lens of legal
culture, drawing in particular on Lawrence Friedman’s distinction between ‘internal’ and ‘external’ legal culture to help understand the factors contributing to the decision. The paper argues that Friedman’s concept
and, in particular, the dialectic between internal and external legal culture, holds much utility at a micro as
well as macro level, in interrogating the cultural logics at work in judicial decision-making
Evidence and absence in the archives: A study of the Irish Refugee Appeals Tribunal Archive to assess the state practice of determining asylum in Ireland
Creating borders and borderlands is a key role of the contemporary state (Mountz,
2010). This dissertation investigates the Irish state agencies that are part of the border
complex and the ways that borders are enforced for those seeking asylum in Ireland.
Specifically, this dissertation examines the Appeals Tribunal Archive (ATA), a digital
archive of refugee and international protection appeal decisions granting or refusing asylum
and refugee status to asylum seekers in Ireland. This archive contains rituals and practices
of the Irish state as the Tribunal determines asylum and ‘processes’ asylum seekers through
national borders. This project uses innovative mixed methods including digital qualitative
analysis, geocomputation, web-scraping, knowledge exchange forums with those affected
by the state asylum process and archival ethnography to carry out a ‘sustained engagement’
(Stoler, 2009) with the archive.
This investigation, like similar investigations of state archives, reveals a landscape of
clarity and shadows: some practices become clear, some remain hidden. For asylum
seekers, the asylum process is murky, chaotic and disorienting. For the researcher, the
asylum process also appears shadowed; rituals and practices become evident from
investigating the archive’s form and content. This project works towards investigating the
practices, knowledges, assumptions and ‘common sense’ of the Appeals Tribunal through
the archive.
In this dissertation I argue that acts and practices of bordering are central aspects of
statecraft, enacted and performed by state agencies and state agents. This research into
state practice opens space to question the judgements documented in the archive through,
among other things, the deep analysis of decisions and the creation of publicly accessible
records and reports of Tribunal practice. The evidence presented in this dissertation shows
the double-sided nature of asylum determination in Ireland. Outwardly, asylum agencies work to maintain compliance with state and international asylum laws; inwardly, asylum
agencies are restricting borders and movement in Ireland and are restricting the rights of
asylum seekers and their claims to protections under law
Variable Future-Time Expression in Spanish: A Comparison between Heritage and Second Language Learners
This paper examines the expression of futurity in Spanish, specifically the periphrastic future (PF), the morphological future (MF), and the present indicative (PI) in heritage language learners (HLLs) and second language learners (L2 learners), a comparison that allowed us to explore whether linguistic experience provides HLLs an advantage over L2 learners in the domain of morphosyntax. These forms (PF, MF, and PI) are regulated by certainty, temporal distance, and the presence of temporal adverbials. Previous research showed that L2 learners acquire some of these linguistic constraints and that HLLs tend to reduce the MF to modal uses. Data from a contextualized acceptability judgment task completed by 46 HLLs and 42 L2ers manipulated for verb form,
certainty, temporal distance, and adverb and revealed that (i) the PF and the MF were generally rated higher than the PI, (ii) HLLs were sensitive to the three linguistic factors examined, while the L2ers’ sensitivity was modulated by proficiency, and, relatedly, (iii) the two groups differed in the effect of proficiency. For the L2 learners, an increase in proficiency led to a closer pattern to that of
monolingual native speakers (only for temporal distance). Differences in exposure to and instruction in Spanish are discussed as possible sources of these differences
What Can L2ers Tell Us about Codeswitching? Mood Selection in Spanish
An increasing amount of research shows that bilinguals that engage in codeswitching (CS) may show different patterns of usage and sensitivity to particular linguistic structures depending on community norms. Additionally, proficiency may play a different role in sensitivity to code-switched utterances depending on speaker background, as well as the structure investigated. In this study, we aim to examine how bilinguals not exposed to CS in the community rate CS vs. unilingual sentences involving mood selection in Spanish. In an online acceptability judgment task (AJT), 20 Spanish L2ers rated sentences containing verbs in the indicative and subjunctive mood in restrictive relative clauses manipulated for the specificity of the antecedent in two separate sessions: a Spanish monolingual mode and a CS session. The L2ers did not show evidence of a CS effect and maintained a mood distinction according to the specificity of the antecedent both in unilingual and codeswitched sentences. These results are in contrast with the results previously reported for Spanish heritage speakers (HSs), where a CS effect is attested in the loss of preference for the subjunctive in nonspecific relative clauses in the CS vs. the monolingual Spanish condition. Additionally, this distinction is found at both lower and higher proficiency levels. The differences between these speakers and HSs are consistent with data from previous research on CS effects on phonology and Det–N switches. We argue that exposure to community norms is necessary for the acquisition of patterns not related exclusively to the grammaticality of switch junctures (I-language)