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Reversible single-crystal to single-crystal phase transformation between a new werner clathrate and its apohost†
No full textIn this work, we report the synthesis and structural characterisation of the ligand 2(pyridin-3-yl)-benzo [de]isoquinoline-1,3(2H)-dione, 5, its isostructural Werner complexes ML4(NCS)2 (L = 5; M = Co(II) and Ni (II)), and five clathrates with three aromatic guests, ML4(NCS)2·2G (M = Co(II) and Ni(II), G = nitrobenzene (NB); M = Co, G = 1,2 dichlorobenzene (1,2-DCB); M = Co(II) and Ni(II), G = o-xylene (OX)). 5 was pre-pared in high yield by condensation in the solid-state (C3S3, Cocrystal Controlled Solid-State Synthesis). The Werner complexes ML4(NCS)2 (M = Co(II) and Ni(II)) (apohosts) were prepared by reacting M(NCS)2 (M = Co(II) and Ni(II)) and 5 in 1-butanol at 60 °C for 24 h.
The Werner clathrates were prepared by reacting M(NCS)2 (M = Co(II) and Ni(II)), G and 5 in 1-butanol at 60 °C for 48–96 h. The clathrates were observed to transform to the apohost ML4(NCS)2 upon heating. CoL4(NCS)2·2NB was subsequently regenerated by
exposing CoL4(NCS)2 to liquid NB at 60 °C for 48 h. This phase change occurred as a single-crystal to single-crystal phase transformation and was studied by single crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. Structural analyses of the apohost CoL4(NCS)2 and its Werner clathrate CoL4(NCS)2·2NB indicated that rotational freedom of the Co-N bonds together with torsional flexibility of the ligand between the imide bond and the pyridine moiety are key to enabling the structural switching induced by exposure to NB or its remova
Navigating the shifting landscapes of HRM
No full textA confluence of mega-trends mean that HR is experiencing disruption and change on an unprecedented scale. This special issue is designed to inform our understanding of these shifting landscapes of HRM. In this overview we detail the broad contextual backdrop of key changes, before providing an overview of the six articles that make up this special issue. The articles cover agile HR, HR disruption, strategic human capital, employee health and safety, HR co-creation and global flexible working arrangements. We conclude by threading key insights together with suggestions on how theory and research might seek to better embrace disruption and navigate the shifting landscapes of HRM. This includes striving for interdisciplinary insight, finding motivation in practice, looking back to go forward, using multiple pathways for understanding, challenging assumptions and accommodating HR agency. The understanding and insight offered in this special issue hold special relevance in the context of the COVID-19 crisis
Family dynamics, fertility cults, and feminist critiques: the reception of Hosea 1–3 through the centuries
No full textThis article examines a number of contested and contentious issues in the reception of Hosea 1–3, exploring how readers through the centuries have engaged with the interpretive challenges found in the initial chapters of this prophetic text. These include (1) debates concerning whether the marriage of Hosea and Gomer should be understood literally or figuratively; (2) questions concerning the identity of the woman in chp. 3 in relation to the events of chp. 1; (3) proposals on how to understand the metaphorical elements related to Hosea’s marriage and Israel’s infidelity; (4) ethical, theological, and rhetorical concerns raised by these chapters, including feminist critiques; (5) the place of Gomer’s children in the opening chapter of the book; (6) the themes and rhetoric of chp. 2, including the punishment and wooing of the wife and Israel; and (7) the role of Hos 1–3 in Jewish and Christian liturgical traditions. This study offers soundings from across historical, religious, and interpretive traditions that give a sense of the wide-ranging ways in which this book has been read and understood through the centuries. In particular, it highlights that while specific questions and issues related to Hosea have persisted through the years, the underlying interpretive assumptions and approaches to these questions have shifted considerably in various historical periods, which in turn has led to considerable diversity in the reception of this prophetic text
cushLEPOR uses LABSE distilled knowledge to improve correlation with human translation evaluations
No full textHuman evaluation has always been expensive while researchers struggle to trust the automatic metrics. To address this, we propose to customise traditional metrics by taking advantages of the pre-trained language models (PLMs) and the limited available human labelled scores. We first re-introduce the hLEPOR metric factors, followed by the Python portable version we developed which achieved the automatic tuning of the weighting parameters in hLEPOR metric. Then we present the customised hLEPOR (cushLEPOR) which uses LABSE distilled knowledge model to improve the metric agreement with human judgements by automatically optimised factor weights regarding the exact MT language pairs that cushLEPOR is deployed to. We also optimise cushLEPOR towards human evaluation data based on MQM and pSQM framework on English-German and Chinese-English language pairs. The experimental investigations show cushLEPOR boosts hLEPOR performances towards better agreements to PLMs like LABSE with much lower cost, and better agreements to human evaluations including MQM and pSQM scores, and yields much better performances than BLEU (data available at url{this https URL})
Detecting seen/unseen objects with reducing response time for multimedia event processing
No full textThe enormous growth of multimedia content in the domain of the Internet of Things (IoT) leads to the challenge of processing multimedia streams in real-time. Thus, the Internet of Multimedia Things (IoMT) is an emerging concept in the field of smart cities. Conventional event-based systems mainly focus on structured events like energy consumption events, RFID tag readings, packet loss events, etc. Existing real-time image processing systems are domain-specific. Multiple applications (like traffic management, security, supervision activities, etc.) within smart cities may require the processing of numerous seen and unseen concepts (unbounded vocabulary). Deep neural network-based techniques are effective for image recognition. The limitation of having to train classifiers for unseen concepts may increase the overall response-time for multimedia-based event processing models. It is not practical to have all trained classifiers or annotated training data available for a large number of unseen concepts. In this thesis, I address the problem of training classifiers online for unseen concepts to answer user queries that include processing multimedia events in minimum response time and maximum accuracy. The contributions of this thesis are manifold. I proposed an IoMT based multimedia event processing model and optimized it for various scenarios of unseen concepts using hyperparameter tuning, transfer learning, and Large Scale Detection through Adaptation (LSDA). I primarily consider You Only Look Once (YOLO), Single Shot MultiBox Detector (SSD), and RetinaNet, in my models, specifically for the case study of object detection. The results indicate that proposed multimedia event processing models achieve accuracy of 66.34% within 2 hours using classifier division and selection approach, 84.28% within 1 hour using hyperparameter tuning, and 95.14% using domain adaptation-based optimization within 30 min of response-time. My final contribution is designing the first and fast detector “UnseenNet”, to train unseen classes using only image-level labels (i.e., no bounding box annotations). My evaluations demonstrate that UnseenNet outperforms the baseline approaches and reduces the training time of >5.5 hours to <5 minutes
Can Google Translate Rewire Your L2 English Processing?
No full textAbstract: In this article, we address the question of whether exposure to the translated output of MT systems could result in changes in the cognitive processing of English as a second language (L2 English). To answer this question, we first conducted a survey with 90 Brazilian Portuguese L2 English speakers with the aim of understanding how and for what purposes they use web-based MT systems. To investigate whether MT systems are capable of influencing L2 English cognitive processing, we carried out a syntactic priming experiment with 32 Brazilian Portuguese speakers. We wanted to test whether speakers re-use in their subsequent speech in English the same syntactic alternative previously seen in the MT output, when using the popular Google Translate system to translate sentences from Portuguese into English. The results of the survey show that Brazilian Portuguese L2 English speakers use Google Translate as a tool supporting their speech in English as well as a source of English vocabulary learning. The results of the syntactic priming experiment show that exposure to an English syntactic alternative through GT can lead to the re-use of the same syntactic alternative in subsequent speech even if it is not the speaker’s preferred syntactic alternative in English. These findings suggest that GT is being used as a tool for language learning purposes and so is indeed capable of rewiring the processing of L2 English syntax
Time for a paradigm change? Incorporating transnational processes into the analysis of the emerging European health-care system
No full textHealth services have long been insulated from the process of European integration. In this article, however, we show that we are witnessing their re-configuration in an emerging EU health-care system. The article uncovers the structuring lines of this system by focusing on three interrelated EU-wide processes influencing the integration of national health-care systems into a larger whole. First, the privatisation of health-care services following the constraints of Maastricht economic convergence and the EU accession criteria; second, health-care worker and patient mobility arising from the free movement of workers and services within the European Single Market; and third, new EU laws and country-specific prescriptions on economic governance that the EU has been issuing following the 2008 financial crisis. The article shows that these processes have helped to construct a European health-care system that is uneven in terms of the distribution of patient access to services and of health-care workers’ wages and working conditions, but very similar in terms of EU economic and financial governance pressures on health care across EU Member States.European Commission Horizon 2020European Research CouncilUniversity College DublinCentre for Advanced Study (CAS)2021-09-08 JG: PDF replaced at author\u27s reques
Using mHealth apps with children in treatment for obesity: Process outcomes from a feasibility study
No full textBackground: Multicomponent family interventions underline current best practice in childhood obesity treatment. Mobilehealth (mHealth) adjuncts that address eating and physical activity behaviors have shown promise in clinical studies.Objective: This study aimed to describe process methods for applying an mHealth intervention to reduce the rate of eating andmonitor physical activity among children with obesity.Methods: The study protocol was designed to incorporate 2 mHealth apps as an adjunct to usual care treatment for obesity.Children and adolescents (aged 9-16 years) with obesity (BMI ≥98th centile) were recruited in person from a weight managementservice at a tertiary health care center in the Republic of Ireland. Eligible participants and their parents received informationleaflets, and informed consent and assent were signed. Participants completed 2 weeks of baseline testing, including behavioraland quality of life questionnaires, anthropometry, rate of eating by Mandolean, and physical activity level using a smart watchand the myBigO smartphone app. Thereafter, participants were randomized to the (1) intervention (usual clinical care+Mandoleantraining to reduce the rate of eating) or (2) control (usual clinical care) groups. Gender and age group (9.0-12.9 years and 13.0-16.9years) stratifications were applied. At the end of a 4-week treatment period, participants repeated the 2-week testing period.Process evaluation measures included recruitment, study retention, fidelity parameters, acceptability, and user satisfaction.Results: A total of 20 participants were enrolled in the study. A web-based randomization system assigned 8 participants to theintervention group and 12 participants to the control group. Attrition rates were higher among the participants in the interventiongroup (5/8, 63%) than those in the control group (3/12, 25%). Intervention participants undertook a median of 1.0 training mealusing Mandolean (25th centile 0, 75th centile 9.3), which represented 19.2% of planned intervention exposure. Only 50% (9/18)of participants with smart watches logged physical activity data. Significant differences in psychosocial profile were observedat baseline between the groups. The Child Behavior Checklist (CBCL) mean total score was 71.7 (SD 3.1) in the interventiongroup vs 57.6 (SD 6.6) in the control group, t-test P<.001, and also different among those who completed the planned protocolcompared with those who withdrew early (CBCL mean total score 59.0, SD 9.3, vs 67.9, SD 5.6, respectively; t-test P=.04). Conclusions: A high early attrition rate was a key barrier to full study implementation. Perceived task burden in combination with behavioral issues may have contributed to attrition. Low exposure to the experimental intervention was explained by poor acceptability of Mandolean as a home-based tool for treatment. Self-monitoring using myBigO and the smartwatch was acceptable among this cohort. Further technical and usability studies are needed to improve adherence in our patient group in the tertiary setting.European Commission Horizon 202
Exploring traditions of professional practice in CRM geoarchaeology: home and away
No full textUCD Fulbright Information session. Dublin, Ireland, 28th September 2017Geoarchaeology comprises a group of approaches used to interpret and predict the archaeological record. Despite a very high level of best practice during Celtic Tiger CRM, for some reason geoarchaeology – a standard practice in CRM in France, UK, Switzerland etc. – was not carried out by Irish contract archaeology.Fullbright - Geological Survey Irelan
Rapid separation of phenolic flavourings by liquid chromatography and nanomolar electrochemical detection at a boron-doped diamond electrode
No full textIn recent years, there has been considerable research focus on natural plant phenolics. They are present as key contributors to the flavour of food and beverages and are also proven to function as antioxidants, providing a wide range of physiological properties including anti-cancer, anti-inflammatory and anti-microbial. Their investigation and detection in plants, food and beverages require the development of rapid, selective and sensitive analytical methods.
In this thesis, an overview of plant secondary metabolites, their classification and physiological properties are given. The characteristics of the boron-doped diamond (BDD) electrode and the coupling of liquid chromatography (LC) with electrochemical detection (ECD) are also described. This work focuses on determining the phenolic analytes that are associated with the distinct flavour of whiskey. Initially, the whiskey is analysed using direct electroanalysis at a Nafion-modified BDD electrode. Inclusion complexation with cyclodextrins (CDs) and peak deconvolution reveals guaiacols, phenols and cresol isomers as the phenolic molecular fingerprint of whiskey. Pre-concentration with Nafion on the electrode surface results in a 5-fold decrease in the limit of detection (LOD) compared to the bare BDD electrode. The electro-oxidation mechanisms of the analytes are also investigated with cyclic voltammetry (CV).
To specifically determine the flavour contributing analytes and to differentiate whiskey based on geographical origin, detection at the BDD electrode is preceded by chromatographic separation with a C18 core-shell column. Significantly higher concentrations of the phenolic compounds are determined in Islay whiskey, attributed to its unique production process. The detection limit (S/N = 3) of guaiacol with LC-ECD is 5 nM, 80-fold lower than that obtained with LC-ultraviolet (UV) detection (2 µM).
Attention was then turned to the separation and detection of gallic acid (GA) and ellagic acid (EA) in whiskey. GA and EA are present in the oak casks used for maturation and so their presence can be used as markers of authentic whiskey. Chromatographic separation using a reversed-phase (RP) C18 column with gradient elution is followed by amperometric detection at a BDD electrode. LODs of 60 and 200 nM are obtained for GA and EA, respectively, with the highest concentrations of both acids found in a 14-year-old whiskey.
Rapid and sensitive analytical methods are required for the detection of spoilage metabolites in the food and beverage manufacturing industries. In beverages, guaiacol may be present as a result of microbial metabolism, resulting in the formation of a medicinal off-odour with subsequent financial implications. LC-ECD at a BDD electrode provides LODs of 10-30 nM for guaiacol and its phenolic precursors. Notably, separation is achieved within 60 s, providing a rapid alternative to traditional microbiological culturing methods.
The outcomes presented represent an advancement in the separation and selective sensing of phenolic analytes, and are of importance in the food and beverage sectors