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Studies in synthesis using CO2 and H2 gases
(University College Cork, 2023) Lowry, Amy; Mcglacken, Gerard P.; Byrne, Peter; Irish Research Council; Higher Education Authority
This thesis is split into two parts based on two different areas of research. Part 1 Part 1 is sub-divided into four chapters. Chapter 1 involves a review of the existing research conducted in this area. Chapter 2 provides details on the research carried out in this project on the development of a Wittig CO2 utilisation methodology for the synthesis of α,β unsaturated carboxylic acids. Chapter 3 involves discussion on the development of protocols for purification of the α,β-unsaturated carboxylic acids synthesised. The Conclusions and Future Work section relating to this area of research is found at the end of Chapter 3. Chapter 4 outlines the experimental work for Part 1. CO2 utilisation continues to capture the attention of chemists due to the ever-increasing levels of CO2 and the negative effects of global warming. CO2 is an inexpensive and environmentally friendly C1 building block, which can be used in the synthesis of value-added chemicals. Many medicinally important compounds and natural products contain the elements of CO2 within their structure, including carboxylic acids, enoates, and carbamates. In particular, α,β unsaturated carboxyl compounds are typically accessed by metal-catalysed transformations or condensation reactions, which often require hydrolysis of the ester product to furnish the corresponding acid. In this project, a telescoped process was developed, that not only achieves CO2 activation, but exploits a novel application of the Wittig reaction, enabling direct installation of the carboxyl group by two successive carbon-carbon bond forming events. Reaction optimisation and purification studies were carried out and 34 α,β-unsaturated carboxylic acids were synthesised using the method, containing a wide range of functional groups, as well as a number of pharmaceutical precursors, in moderate to excellent yields. As part of this work, a novel method for purification of α,β-unsaturated carboxylic acids was developed. Part 2 Part 2 is sub-divided into three chapters. Chapter 5 involves a discussion on the background of the project and a review of the existing research conducted in the area. Chapter 6 involves a discussion of the research carried out in this project on the dearomatisation of benzofuroquinolines by a Pd-catalysed hydrogenation reaction. The Conclusions and Future Work section relating to this part of the thesis is found at the end of Chapter 6. Chapter 7 outlines the experimental work for Part 2. Within the McGlacken group, development of C-H activation methodologies has been a large area of research, and, in particular, benzofuroquinolines have been synthesised via direct intramolecular arylation of 4-phenoxyquinolines. The quinoline nucleus is one of the most frequently occurring ring systems in approved drugs, and hydrogenation of the quinoline nucleus and the selectivity thereof, has been reported in the literature. In addition, increasing interest in the concept of ‘escaping flatland’, whereby the saturation of compounds is increased, allowing for the exploration of more architecturally complex molecules that will potentially give rise to enhanced biological activities. In this part of the thesis, a range of differently substituted benzofuroquinolines were hydrogenated to generate 18 selectively dearomatised benzofuroquinolines. Investigations were carried out into different reaction conditions tolerated by the reaction, and the fate of halogen substituents in the reaction. In addition, a double reduction product side-product was identified and characterised, opening up the methodology to the formation of a new class of novel compounds.
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Cás-staidéir ar logainmneachaibh agus ar threabhainmneachaibh dar tús ‘L’ ó fhoinsíbh Gaoluinne agus Laidine idir c.400-c.1800 A.D.
(University College Cork, 2022) Ó Cionnfhaolaidh, Cian; Murray, Kevin; Nic Cárthaigh, Emma; Brian Mac Cárthaigh; Bord Stiúrthóirí FEXCO; St. Finnian's Trust
Deintear iarracht sa tráchtas so iniúchadh deimhin a dhéanamh ar réimse ainmneacha stairiúla dar tús ‘L’, idir logainmneacha is treabhainmneacha, a thagann ó achainníbh Gaoluinne agus Laidin na hÉireann a bhaineann leis an dtréimhse 400-1800. Do bhailíos na hainmneacha so agus dheineas anailís ortha le linn mo thréimhse oibre leis an dTionscnamh Locus. Is é cuspóir an tionscnaimh so foclóir áitainmnaíoch is treabhainmníoch a chur ar fáil ar a dtugtar, Historical Dictionary of Gaelic Placenames [HDGP]. Cuirfear an foclóir so in áit an Onomasticon Goedelicum (OnomG) le hEdmund Hogan: .i. an seana-fhoclóir. Roghnaíog na hainmneacha a chuireag san áireamh sa tráchtas de réir ord aibítre na n-ainmneacha mar atháid leagaithe amach ins an OnomG féinig go ginearálta; agus de réir sean-achainní a bhfuil innéacsanna acu agus flúirse sean-ainmneacha ionta, mar athá, inter alia, na hannála, e.g. Annála Uladh; na geinealaigh, e.g. Corpus Genealogiarum Hiberniae; Lebor Gabála Érenn agus Lebor na Cert. Ina theannta san, bhailíog agus dheineag anailís ar roinnt ainmneacha eile sa tráchtas so nár iniaigh Hogan, mar athá ag teacht le polasaí Thionscaimh Locus féinig, m.sh. na Hardiman Legal Deeds. I gcorp an tráchtais mar san, tugtar ceann-iontrálacha na n-ainmneacha féinig ar dtúis mar a fhoilseofar amach anso mar chuid de HDGP. Díreach i ndiaidh gach ceann-iontrála, tugtar tráchtaireacht ina ndeintear plé ar bhrí agus ar mholtaíbh mar gheall ar shuíomh na hainme athá fé chaibideal. I gcás na n-iontrálacha, tháid scrite i mBéarla toisc gurb é sin teanga an fhoclóra HDGP agus léirítear brí agus suíomh na n-ainmneacha ar dtúis. Soláthraítear tagairtí na n-ainmneacha féinig ansan agus iad curtha leis an iontráil go croineolaíoch agus iad roinnte le fo-theidealaibh ar bhonn théamaí comhchoitinne a gheibhtear i measc na dtagairtí féinig: ‘Traditional derivation’, ‘Early references’, ‘Genealogical references’, ‘Short form’ srl. Ag deireadh na hiontrála ansan, tugtar na hachainní tánaisteacha ina bpléitear ainm na hiontrála, mar aon le cros-tagairtíbh do leaganachaibh éagsúla na hainme san agus ainmneacha gaolmhara eile. I dtaobh na tráchtaireachta ansan, deintear gach iarracht aoinní a thabharfadh brí, suíomh nú foirmeacha éagsúla na n-ainmneacha le fios a phlé. Mar aon le haird a thabhairt ar fhoinsíbh tánaisteacha, baintear feidhm as roinnt modhanna go háirithe le haghaidh suímh na n-ainmneacha dh’fhuascailt. Mar shampla, is minic a chuirtear na tagairtí féinig i gcomparáid lena chéile, mar aon le comhthéacs téacsúil na hachainne a thuiscint, e.g. an chuid den dtéacs ina luaitear an ainm féineach a ghéirléamh do leideannaibh mar gheall ar shuíomh na hainme sin. Má luaitear ainmneacha eile sa téacs i dteannta na hainme athá fé chaibideal, deintear iarracht iadsan dh’aimsiú chón maith d’fhonn suímh na hainme féinig a chúngú nú a thriantánú. Baintear leas as léarscáileannaibh nua-aimseartha na Suirbhéireachta Ordanáis mar aon le ceannaibh stairiúla eile cosúil le léarscáileannaibh Grand Jury le Pelham agus léarscáileanna de chuid Petty sa chúram so chón maith. In ainneoin mo sheacht ndícheall suíomh ainmneacha a mheas, is minic nach féidir ach moltaí a thabhairt agus ráiníonn sé ar uairibh eile ná bím inniúil ar mholadh a thabhairt fiú. Tháid na hiontrálacha sa tráchtas roinnte i gceithre caibideal. Caibideal a hAon a dhíríonn ar na hainmneachaibh dar tús ‘L’ mar a gheibhtear iad sna Hardiman Legal Deeds amháin, mar athá Leathbhaile, Leathcheathramha, Lios agus Longphort. I gCaibideal a Dó, tugtar aghaidh ar onomata ó réimse leathan foinsí gur gnéithe topagrafaíocha iad. Mar athá: Labhrann, Lachtmhagh, Ladhrann, Lagán, Lag an Choire, Lathach, Leac, Leaca(in), Leithead, Leithghleann, Leitir Luighne, Liathghort agus Liathmhagh. I gCaibideal a Trí, tugtar fé dhéin na Laoigheas agus na fodhreamanna a bhain leo. I gCaibdeal a Ceathair ansan, tugtar iontrálacha do roinnt aitheachthuatha dar tús ‘L’: .i.. Ladraighe, Liobha(r)traighe, Lu(i)dhr(a)ighe, Lu(i)sr(a)ighe, a thagann ó Leagan a hAon de Tairired na nDéssi agus na liostaí / tráchtaireachtaí treabhchais; agus an ainm Ladhg(h)mainn a gheibhtear in Annála Ríoghachta Éireann, Annála Inis Faithlinn, Leabhar Muimhneach agus Leabhar Mór na nGeinealach. Mar a chítear anso, thá an tráchtas scartha i ndá rann ina ndírítear ar logainmneachaibh sa chéad chuid de, .i. Caidbideal a hAon is a Dó, agus ar threabhainmneachaibh sa tara cuid, .i. Caibideal a Trí is a Ceathair.
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Development of a personalized multiclass classification model to detect blood pressure variations associated with physical or cognitive workload
(MDPI, 2024-06-06) Valerio, Andrea; Demarchi, Danilo; O'Flynn, Brendan; Motto Ros, Paolo; Tedesco, Salvatore; Enterprise Ireland; Science Foundation Ireland; European Regional Development Fund
Comprehending the regulatory mechanisms influencing blood pressure control is pivotal for continuous monitoring of this parameter. Implementing a personalized machine learning model, utilizing data-driven features, presents an opportunity to facilitate tracking blood pressure fluctuations in various conditions. In this work, data-driven photoplethysmograph features extracted from the brachial and digital arteries of 28 healthy subjects were used to feed a random forest classifier in an attempt to develop a system capable of tracking blood pressure. We evaluated the behavior of this latter classifier according to the different sizes of the training set and degrees of personalization used. Aggregated accuracy, precision, recall, and F1-score were equal to 95.1%, 95.2%, 95%, and 95.4% when 30% of a target subject’s pulse waveforms were combined with five randomly selected source subjects available in the dataset. Experimental findings illustrated that incorporating a pre-training stage with data from different subjects made it viable to discern morphological distinctions in beat-to-beat pulse waveforms under conditions of cognitive or physical workload.
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Design of a multi-sensors wearable system for continuous home monitoring of people With Parkinson's
(IEEE, 2024-03-11) Sica, Marco; Varnosfaderani, Omid Talebi; Crowe, Colum; Kenny, Lorna; Bocchino, Andrea; O'Flynn, Brendan; Mueller, David Scott; Tedesco, Salvatore; Timmons, Suzanne; Barton, John; Enterprise Ireland; AbbVie; Science Foundation Ireland; European Regional Development Fund
Parkinson’s disease is a degenerative neurological disorder that impairs motor functions and is accompanied by a wide range of non-motor symptoms, such as sleep problems. Parkinsonism is assessed during clinical evaluations and via self-administered diaries and, based on these, the required medication therapies are provided to lessen symptoms. Tri-axial accelerometers and gyroscopes have the potential utility to objectively assess the patient’s condition and aid clinicians in their decision-making. People with Parkinson’s often have significant abnormalities in blood pressure due to comorbid age-related cardiovascular disease and orthostatic hypotension, which result in blurred vision, dizziness, and falls. Frequent blood pressure monitoring may aid in the evaluation of such events and differentiate Parkinson’s disease symptoms from those originated by hypotension. In the present paper, a novel technology for the remote monitoring of Parkinsonian symptoms is presented: the WESAA system. It consists of two devices, worn on the wrist and ankle; its main function is to record accelerations and angular velocities from these body parts, together with photoplethysmograph and electrocardiogram data. This information can be elaborated offline to measure common Parkinson’s disease motor symptoms (e.g., tremor, bradykinesia, and dyskinesia), as well as gait speed, sleep-wake cycles, and cuff-less blood pressure measurements. The overall system requirements, market overview, industrial design and ergonomics, system development, user experience, early results of the gathered inertial raw data, and validation of the photoplethysmograph and electrocardiogram signal waveforms are all thoroughly discussed. The developed technology satisfies all system requirements, and the sensors adopted provided outcomes comparable with gold standard techniques.
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A dataset for fatigue estimation during shoulder internal and external rotation movements using wearables
(Springer, 2024-04-27) Yasar, Merve Nur; Sica, Marco; O'Flynn, Brendan; Tedesco, Salvatore; Menolotto, Matteo; Science Foundation Ireland; European Regional Development Fund
Wearable sensors have recently been extensively used in sports science, physical rehabilitation, and industry providing feedback on physical fatigue. Information obtained from wearable sensors can be analyzed by predictive analytics methods, such as machine learning algorithms, to determine fatigue during shoulder joint movements, which have complex biomechanics. The presented dataset aims to provide data collected via wearable sensors during a fatigue protocol involving dynamic shoulder internal rotation (IR) and external rotation (ER) movements. Thirty-four healthy subjects performed shoulder IR and ER movements with different percentages of maximal voluntary isometric contraction (MVIC) force until they reached the maximal exertion. The dataset includes demographic information, anthropometric measurements, MVIC force measurements, and digital data captured via surface electromyography, inertial measurement unit, and photoplethysmography, as well as self-reported assessments using the Borg rating scale of perceived exertion and the Karolinska sleepiness scale. This comprehensive dataset provides valuable insights into physical fatigue assessment, allowing the development of fatigue detection/prediction algorithms and the study of human biomechanical characteristics during shoulder movements within a fatigue protocol.