Exploring the relationship between patterns of physical activity, sedentary behaviour and cardiometabolic health in middle-aged Irish adults

Background and Study Rationale Being physically active is a major contributor to both physical and mental health. More specifically, being physically active lowers risk of coronary heart disease, high blood pressure, stroke, metabolic syndrome (MetS), diabetes, certain cancers and depression, and increases cognitive function and wellbeing. The physiological mechanisms that occur in response to physical activity and the impact of total physical activity and sedentary behaviour on cardiometabolic health have been extensively studied. In contrast, limited data evaluating the specific effects of daily and weekly patterns of physical behaviour on cardiometabolic health exist. Additionally, no other study has examined interrelated patterns and minute-by-minute accumulation of physical behaviour throughout the day across week days in middle-aged adults. Study Aims The overarching aims of this thesis are firstly to describe patterns of behaviour throughout the day and week, and secondly to explore associations between these patterns and cardiometabolic health in a middle-aged population. The specific objectives are to: 1 Compare agreement between the International Physical Activity Questionnaire-Short Form (IPAQ-SF) and GENEActiv accelerometer-derived moderate-to-vigorous (MVPA) activity and secondly to compare their associations with a range of cardiometabolic and inflammatory markers in middle-aged adults. 2 Determine a suitable monitoring frame needed to reliably capture weekly, accelerometer-measured, activity in our population. 3 Identify groups of participants who have similar weekly patterns of physical behaviour, and determine if underlying patterns of cardiometabolic profiles exist among these groups. 4 Explore the variation of physical behaviour throughout the day to identify whether daily patterns of physical behaviour vary by cardiometabolic health. Methods All results in this thesis are based on data from a subsample of the Mitchelstown Cohort; 475 (46.1% males; mean aged 59.7±5.5 years) middle-aged Irish adults. Subjective physical activity levels were assessed using the IPAQ-SF. Participants wore the wrist GENEActiv accelerometer for 7 consecutive days. Data was collected at 100Hz and summarised into a signal magnitude vector using 60s epochs. Each time interval was categorised based on validated cut-offs. Data on cardiometabolic and inflammatory markers was collected according to standard protocol. Cardiometabolic outcomes (obesity, diabetes, hypertension and MetS) were defined according to internationally recognised definitions by World Health Organisation (WHO) and Irish Diabetes Federation (IDF). Results The results of the first chapter suggest that the IPAQ-SF lacks the sensitivity to assess patterning of activity and guideline adherence and assessing the relationship with cardiometabolic and inflammatory markers. Furthermore, GENEActiv accelerometer-derived MVPA appears to be better at detecting relationships with cardiometabolic and inflammatory markers. The second chapter examined variations in day-to-day physical behaviour levels between- and within-subjects. The main findings were that Sunday differed from all other days in the week for sedentary behaviour and light activity and that a large within-subject variation across days of the week for vigorous activity exists. Our data indicate that six days of monitoring, four weekdays plus Saturday and Sunday, are required to reliably estimate weekly habitual activity in all activity intensities. In the next chapter, latent profile analysis of weekly, interrelated patterns of physical behaviour identified four distinct physical behaviour patterns; Sedentary Group (15.9%), Sedentary; Lower Activity Group (28%), Sedentary; Higher Activity Group (44.2%) and a Physically Active Group (11.9%). Overall the Sedentary Group had poorer outcomes, characterised by unfavourable cardiometabolic and inflammatory profiles. The remaining classes were characterised by healthier cardiometabolic profiles with lower sedentary behaviour levels. The final chapter, which aimed to compare daily cumulative patterns of minute-by-minute physical behaviour intensities across those with and without MetS, revealed significant differences in weekday and weekend day MVPA. In particular, those with MetS start accumulating MVPA later in the day and for a shorted day period. Conclusion In conclusion, the results of this thesis add to the evidence base regards an optimal monitoring period for physical behaviour measurement to accurately capture weekly physical behaviour patterns. In addition, the results highlight whether weekly and daily distribution of activity is associated with cardiometabolic health and inflammatory profiles. The key findings of this thesis demonstrate the importance of daily and weekly physical behaviour patterning of activity intensity in the context of cardiometabolic health risk. In addition, these findings highlight the importance of using physical behaviour patterns of free-living adults observed in a population-based study to inform and aid health promotion activity programmes and primary care prevention and treatment strategies and development of future tailored physical activity based interventions.

Vidéos contre lectures: Une évaluation de l'utilisation de vidéos pour accomplir la construction initiale de connaissances

Abstract : The goal of this study was to determine whether providing videos for students to watch before class would be more effective than assigning readings. The study took place within a flipped classroom: a methodology designed to engage students in the initial construction of knowledge before class, freeing up classroom time for active learning pedagogies. Preparing for class by watching videos should require less of the students’ time than doing readings, and they should respond better to videos than to readings because these more closely mimic this generation’s interactions with information and media. Consequently, flipped classroom students provided with videos should perceive a lower workload, which could translate into more positive learning outcomes. From an instructor’s perspective, however, developing and organizing videos is extremely time consuming. Thus, a teacher giving consideration to flipping their class would likely want to know whether videos would lead to positive outcomes for their students before actually committing to developing these. However, no research to date was identified which has examined the question of whether flipped class videos would be more effective than readings. The hypotheses for the study were that videos would result in measurable learning gains for the students, and would lead to lower time demands and perceived workloads, as well as more positive attitudes. These were tested using a quasi-experimental design involving a convenience sample of two small college General Biology 1 courses taught by the same teacher. One group had videos to watch before class for the first 1/3 of the course (treatment; Class A), during which the other was assigned readings (control; Class B). Following this, both groups were provided with videos. Student scores were compared on pre-instruction and in-class quizzes, activities, four unit tests, and a final exam. Further, students completed a 44 item survey as well as a demographic questionnaire. Results suggest greater learning gains for students provided with videos. Certainly, students from Class B improved significantly when provided with videos, especially as compared to Class A, whose improvement over the same time span was marginal. However, conclusions based on these results are somewhat tentative, as Class A performed rather poorly on all summative assessments, and this could have driven the patterns observed, at least partially. From the surveys, Class B students reported that they spent more time preparing for class, were less likely to do the necessary preparations, and generally perceived their effort and workload levels to be higher. These factors were significant enough that they contributed to four students from Class B (10% of the class) dropping the course over the semester. In addition, students from both groups also reported more positive attitudes towards videos than readings, although they did not necessarily feel that videos were (or would be) a more effective study and learning tool. The results of this study suggest that any effort on the part of an instructor to prepare or organize videos as pre-class instructional tools would likely be well spent. However, even outside of the context of a flipped classroom, this study provides an indication that assigned readings can place heavy workload requirements on students, which should give cause for any instructor employing mandatory readings to reassess their approach. Finally, since both groups were statistically equivalent across all measured demographic variables, it appears that some of the observed disparities in assessment scores may have been driven by differences in group dynamics. Consequently, the suggestion is made that an instrument to measure classroom climate should be incorporated into any research design comparing two or more interacting groups of students, as group dynamics have the potential to play a key role in any outcomes.||Résumé : L'objectif de cette étude était de déterminer si fournir des vidéos aux étudiants avant une classe serait plus efficace comme méthode d’apprentissage individuel que de leur donner une liste de lectures à compléter. L'étude a eu lieu dans une classe renversée – une stratégie plus reconnu sous le nom de «classroom flipping» – ce qui ce trouve à être une méthodologie qui vise à obliger les élèves d’accomplir le transfert de connaissances initial avant la classe, en vue de libérer du temps de classe pour des activités pédagogiques plus approfondie. En théorie, pour les élèves, se préparer pour une classe renversé en regardant des vidéos devrait exiger moins de temps que d’être obligé à apprendre le matériel en lisant. En plus, présenter le matériel d’un cours avec des vidéos imite de plus près les genres d’interactions qu’on les étudiants de cette génération avec de l'information et les médias, ce qui devrait faciliter leur tâche. Par conséquent, les élèves d’une classe renversée fournies avec des vidéos devraient percevoir une charge de travail moins élevée, et ceci pourrait se traduire en bilans d'apprentissage plus positifs. Cependant, du point de vue du professeur, avoir à développer et organiser des vidéos se présente comme un gros défi, surtout en vue du temps et de l’effort qui sont requis. Ainsi, un enseignant qui songe à renversée sa classe voudrait probablement savoir si le fait d’offrir des vidéos mène à des résultats positifs avant de réellement s'engager dans le développement de ces derniers. Par contre, lors de l’écriture de ce texte, aucune étude n’a été identifié qui répond à cette question, et aucune publication compare la performance des étudiants lorsqu’ils ont des vidéos à regarder avec lorsqu’ils sont obligés de faire de la lecture pour se préparer. Alors, les hypothèses de l'étude étaient que des étudiants ayant accès à des vidéos démontreraient des gains d’apprentissages évidents, qu’ils apercevraient des requêtes de temps moins encombrantes et une charge de travail plus faible, et, en vue de ces derniers, que les étudiants auraient des attitudes plus positives envers le cours et le matériel. Les hypothèses ont été testés à l'aide d'un modèle quasi-expérimental, avec comme échantillon deux classes collégiales de Biologie générale 1, tout les deux enseignés par le même professeur. Un de ces groupes avaient accès à des vidéos pour se préparer pour chaque classe lors du premier tiers du cours, alors que l’autre groupe étaient obligé de faire de la lecture. Après le premier tiers du cours, ce qui fut 10 des 30 classes du semestre, les deux groupes ont été fournis avec des vidéos pour le restant du cours. Des notes ont été ramassées et comparées sur des mini-examens préparatoires avant et durant les classes, sur des activités complétées en classe, sur quatre examens en classe, et un examen final. En outre, les étudiants ont rempli un questionnaire composé de 44 items, ainsi qu’un autre questionnaire démographique. Les résultats de l’étude suggèrent qu’une décision d’offrir des vidéos aux élèves peut mener à des gains d'apprentissage plus élevés comparativement à l’option lecture. En particulier, les élèves du groupe initial de lecture se sont considérablement améliorées lorsqu'ils ont été fournis avec des vidéos, surtout par rapport au groupe initial de vidéos, dont l’amélioration durant la même période était marginale. Cependant, ces conclusions sont un peu incertaines, parce que la performance du groupe initial de vidéos était globalement médiocre, ce qui aurait pu mener aux résultats observés. Par contre, les résultats obtenus des questionnaires étaient moins incertains, et indiquent que les élèves qui se sont vues attribués des lectures passaient plus de temps pour préparer leurs classes, étaient plus aptes à ne pas faire les préparatifs nécessaires, et ont aperçus leurs niveaux d'efforts et leurs charges de travails comme étant plus élevés. Ces facteurs étaient suffisamment importants qu'ils ont contribué au fait que quatre étudiants du groupe de lecture, soit 10% de la classe, ont abandonnés le cours durant le premier tiers du semestre. Finalement, les élèves ont démontrés des attitudes plus positives envers les vidéos, bien qu'ils ne trouvaient pas nécessairement que ceux-ci étaient plus efficaces que les lectures lorsqu’ils voulaient étudier pour les examens. Basé sur ces résultats, il est possible de conclure que tout effort de la part d'un instructeur pour préparer ou organiser des vidéos pédagogiques serait probablement un bon investissement. En plus, et même en dehors du contexte d'une classe renversée, cette étude offre une indication qu’une stratégie pédagogique qui oblige les étudiants à faire beaucoup de lecture peut imposer des exigences et une charge de travail très élevée pour les étudiants, ce qui devrait donner cause à tout instructeur qui attribue des lectures à réévaluer leur approche. Enfin, puisque les deux groupes étaient équivalents d’un point de vue statistique sur toutes les mesures démographiques, il semble que certaines disparités entre les deux groupes dans les notes d'évaluation et d’examens peuvent possiblement avoir été entraînées par des différentes dynamiques dans chaque group. Par conséquent, il est suggéré que des mesures de relations entre étudiants et de dynamiques de groupes devraient être incorporé dans n’importe qu’elle recherche comparant deux ou plusieurs groupes d’étudiants, et surtout quand ces étudiants sont en interaction, parce-que en toute apparence les dynamiques de groupes ont le potentiel de jouer un rôle clé dans les résultats obtenus.

Developmental and physical-fitness associations with gross motor coordination problems in peruvian children

he aims of this cross-sectional study were to examine the developmental characteristics (biological maturation and body size) associated with gross motor coordination problems in 5193 Peruvian children (2787 girls) aged 6–14 years from different geographical locations, and to investigate how the probability that children suffer with gross motor coordination problems varies with physical fitness. Children with gross motor coordination problems were more likely to have lower flexibility and explosive strength levels, having adjusted for age, sex, maturation and study site. Older children were more likely to suffer from gross motor coordination problems, as were those with greater body mass index. However, more mature children were less likely to have gross motor coordination problems, although children who live at sea level or at high altitude were more likely to suffer from gross motor coordination problems than children living in the jungle. Our results provide evidence that children and adolescents with lower physical fitness are more likely to have gross motor coordination difficulties. The identification of youths with gross motor coordination problems and providing them with effective intervention programs is an important priority in order to overcome such developmental problems, and help to improve their general health status.

Study of Rapid Alkalinization Factor (RALF)genes as plant susceptibility agents during plant-pathogen interaction in strawberry

Rapid Alkalinization Factor (RALF) are cysteins-rich peptides ubiquitous in plant kingdom. They play multiple roles as hormone signals and recently their involvement in host-pathogen crosstalk as negative regulator of immunity in Arabidopsis has also been recognized. In addition, RALF homologue peptides are secreted by different fungal pathogens as effectors during early stages of infections. The aim of this work was to characterize RALF genes as susceptibility factors during plant pathogen interaction in strawberry. For this, the genomic organization of the RALF gene families in the octoploid strawberry (Fragaria × ananassa) and the re-annotated genome of Fragaria vesca were described , identifying 13 member in F. vesca (FvRALF) and 50 members in F. x ananassa (FaRALF). The changes in expression of fruit FaRALF genes was investigated upon infection with C.acutatum and B. cinerea showing that, among RALF genes expressed in fruit, FaRALF3 was the only one upregulated by fungal infection in the ripe stage. A role of FaRALF3 as susceptibility gene was then assessed trough Agrobacterium-mediated transient FaRALF3 overexpression and silencing in fruits, revealing that FaRALF3 expression promotes fungal growth and hyphae penetration in host tissues. In silico analysis was used to identify distinct pathogen inducible elements upstream of the FaRALF3 gene. Agroinfiltration of strawberry fruit with deletion constructs of the FaRALF3 promoter identified a 5’ region required for FaRALF3 expression in fruit, but failed to identify a region responsible for fungal induced expression. Furthermore, FaRALF3 and strawberry receptor FERONIA (FaMRLK47) were heterologously expressed in E. coli in order to purify active proteins forms and study RALF-FERONIA interaction in strawberry. However, it was not possible to obtain pure and active proteins. Finally RNAi transgenic plants silenced for the FvRALF13 gene were genotypically and phenotypically characterized suggesting a role of FvRALF13 in flowering time regulation and reproductive organs development.

New Metal Tetrazolate Complexes: Design, Synthesis, Characterization and Applications

This final thesis is aimed at summarizing the research program I have carried out during my PhD studies, that has been dealing with the design, the preparation, characterization and applications of new Re(I), Ru(II), and Ir(III) metal complexes containing anionic ligands such as 5-aryl tetrazolates [R-CN4]- or their neutral analogues, N-alkyltetrazoles [R-CN4-R1]. Chapter 1 consists of a brief introduction on tetrazoles and metal-tetrazolato complexes, and on the photophysical properties of d6 transition metal complexes. In chapter 2, the synthesis, characterization and study of the photophysical properties of new luminescent Ir(III)-tetrazolate complexes are discussed. Moreover, the application of one of the new Ir(III)-CN complexes as emissive core in the fabrication of an OLED device is reported. In chapter 3, the study of the antimicrobial activity of new Ru(II)-alkyltetrazole complexes is reported. When the pentatomic ring was substituted with a long alkyl residue, antimicrobial activity toward Deinococcus radiodurans was observed. In chapter 4, a new family of luminescent Re(I)-tetrazolate complexes is reported. In this study, different N-alkyl tetrazoles play the role of diimine (diim) ligands in the preparation of new Re(I) tricarbonyl complexes. In addition, absorption and emission titration experiments were performed to study their interaction with Bovine Serum Albumin (BSA). In chapter 5, the synthesis and characterization of new luminescent Re(I)-tetrazolate complexes are discussed. The use of sulfonated diimine ligands in the preparation of new Re(I) tricarbonyl complexes led to the first example Re(I) complexes for the luminescent staining of proteins. In chapter 6, the synthesis, a new family of Ir(III)-NO2 tetrazole complexes displaying unexpected photophysical properties are discussed. Moreover, the possibility to tune the luminescent output of such systems upon chemical modification of the pending nitro group was verified by performing reduction tests with sodium dithionite; this represents encouraging evidence for their possible application as hypoxia-responsive luminescent probes in bioimaging.

The educational problem that MOOCs could solve: professional development for teachers of disadvantaged students

The demographics of massive open online course (MOOC) analytics show that the great majority of learners are highly qualified professionals, and not, as originally envisaged, the global community of disadvantaged learners who have no access to good higher education. MOOC pedagogy fits well with the combination of instruction and peer community learning found in most professional development. A UNESCO study therefore set out to test the efficacy of an experimental course for teachers who need but do not receive high-quality continuing professional development, as a way of exploiting what MOOCs can do indirectly to serve disadvantaged students. The course was based on case studies around the world of information and communication technology (ICT) in primary education and was carried out to contribute to the UNESCO “Education For All” goal. It used a co-learning approach to engage the primary teaching community in exploring ways of using ICT in primary education. Course analytics, forums and participant surveys demonstrated that it worked well. The paper concludes by arguing that this technology has the power to tackle the large-scale educational problem of developing the primary-level teachers needed to meet the goal of universal education.

Distributed optimization and games over networks: a system theoretical perspective

Several decision and control tasks involve networks of cyber-physical systems that need to be coordinated and controlled according to a fully-distributed paradigm involving only local communications without any central unit. This thesis focuses on distributed optimization and games over networks from a system theoretical perspective. In the addressed frameworks, we consider agents communicating only with neighbors and running distributed algorithms with optimization-oriented goals. The distinctive feature of this thesis is to interpret these algorithms as dynamical systems and, thus, to resort to powerful system theoretical tools for both their analysis and design. We first address the so-called consensus optimization setup. In this context, we provide an original system theoretical analysis of the well-known Gradient Tracking algorithm in the general case of nonconvex objective functions. Then, inspired by this method, we provide and study a series of extensions to improve the performance and to deal with more challenging settings like, e.g., the derivative-free framework or the online one. Subsequently, we tackle the recently emerged framework named distributed aggregative optimization. For this setup, we develop and analyze novel schemes to handle (i) online instances of the problem, (ii) ``personalized'' optimization frameworks, and (iii) feedback optimization settings. Finally, we adopt a system theoretical approach to address aggregative games over networks both in the presence or absence of linear coupling constraints among the decision variables of the players. In this context, we design and inspect novel fully-distributed algorithms, based on tracking mechanisms, that outperform state-of-the-art methods in finding the Nash equilibrium of the game.

Association between pre-treatment indicators and compliance to neoadjuvant/perioperative chemotherapy in operable gastric cancer

Background and aims: perioperative treatment is currently the gold standard approach for locally advanced gastric cancer (GC). Unfortunately, the phenomenon of patients dropping out of treatment has been frequently observed. The primary aims of this study were to verify if routine blood parameters, the inflammatory response markers, sarcopenia, and the depletion of adipose tissues were associated with compliance with neoadjuvant/perioperative chemotherapy. Methods and study design: sarcopenia and adipose indices were calculated with a CT scan before starting chemotherapy and before surgery. Blood samples were considered before the first and second cycles of chemotherapy. Results: A total of 84 patients with localized operable GC, were identified between September 2010 and January 2021. Forty-four patients (52.4%) did not complete the treatment according to the number of cycles planned/performed. Eight patients (9.5%) decided to suspend chemotherapy, seven patients (8.3%) discontinued because of clinical decision-making, 14 patients (16.7%) because of toxicity, and 15 patients (17.9%) for miscellaneous causes. Sarcopenia before starting chemotherapy was found to be present in 38 patients (50.7%) while it was in 47 patients (60%) at the CT scan before the gastrectomy. In multivariable analysis, both for changes tending to have a value of PLR at basal and in the second control a higher one than the cut-off (OR = 5.03, 95% CI: 1.34 - 18.89, p-value = 0.017), and for PLR which increased from a lower to a higher value in second control with respect to the cut off (OR = 4.64, 95% CI: 1.02 -21.02, p-value = 0.047) resulted associated with incomplete compliance. Conclusions: among the biological indicators, changes in the value of PLR with a tendency towards increasing compared to the cut-off appear to be an immediate indicator of incomplete compliance with neoadjuvant/perioperative treatment. More information is needed to reduce the causes of interruption.

“Clinical and biological role of adjuvant dendritic cells vaccination in newly glioblastoma patients”

Background. Glioblastoma (GBM) is the most common primary tumor of central nervous system and it has a poor prognosis. Standard first line treatment, which includes surgery followed by adjuvant radio-chemotherapy,produces only modest benefits to survival. The interest for immunotherapy in this field derives from the development of new drugs and effective therapies as immune-check points inhibitors, adoptive T-cell approaches or dendritic cell (DC) based vaccines or a combinations of these. GBM is described as a typical “immune-deserted” cancer exhibiting a number of systemic and environmental immunosuppressive factors. Considering the role of microenvironment, and above all the lower tumor load and depletion of immunosuppressive cells in GBM, our hypothesis is that DC vaccine may induce an immune response. Main aims and study design. The main aim of this project is to study the role of immune system in GBM, including identification of potential prognostic and predictive markers of outcome and response to dendritic cell vaccine. Firstly, we performed a retrospective analysis on blood samples. Then, we analyzed the immuno-component in tissues samples of enrolled patients; and compared that with blood results. Then, the last part of the project is based on a prospective clinical trial on patients enrolled in DC-based vaccination produced at IRST Cell Factory and actually used for patients with melanoma and other tumors. The enrollment is still ongoing. Expected results. The project will i) develop an immune-panel of prognostic and predictive markers to help clinicians to improve the therapeutic strategy for GBM patients; ii) provide preliminary results on the effectiveness of immunotherapy on GBM patients.

Kinetic and mechanistic studies on peroxidation and stabilization of lipids with industrial and biological relevance

Lipid peroxidation is a complex mechanism that causes the degradation of lipid material of both industrial and biological significance. During processing, it is known that thermal stress produces oxidation and polymerization of oils. Additionally, biological lipids with both structural and bioactive roles are prone to peroxidation, which can have pathogenic effects including cancer and long-term degenerative disorders. To create innovative strategies to slow down the deterioration of lipids, it is crucial to improve our understanding of oxidation reactions and kinetics. To this purpose, Chapter II of this thesis focuses on the kinetic study of the oxidation reactions that take place during the thermal processing of bio-oils for industrial application. Through a new method it was possible to evaluate the kinetic parameters of oxidation of various lipid materials. This allowed us to distinguish between the different lipid materials based on their intrinsic properties. The effect of 18 antioxidants from the major families of natural and synthetic phenols were studied using the same methodology in order to acquire crucial data for enhancing the antioxidant activity of phenols based on structure-activity at high temperatures. Finally, it has been described how the antioxidant activity of α-tocopherol, revealed to be scarce in our conditions, can be improved in the presence of gamma-terpinene, through a synergistic action. Chapter III describes the synthesis and study of the antioxidant activity of polydopamine nanoparticles, in order to clarify the unclear mechanism of action of this material. Finally, in Chapter IV it was reported how the gamma-terpinene strongly inhibits the peroxidation of unsaturated lipids in heterogeneous model systems (micelles and liposomes) by forming hydroperoxyl radicals which diffuse outside the lipid nucleus, blocking the propagation of the chain radical. Furthermore, gamma-terpinene shows a very potent protective activity against ferroptosis being effective in the nanomolar range in the human neuroblastoma cell model.

Fluorogenic hyaluronan-based probe: characterization and use in advanced microscopy

Among all, the application of nanomaterials in biomedical research and most recently in the environmental one has opened the fields of nanomedicine and nanoremediation. Sensing methods based on fluorescence optical probe are generally requested for their selectivity, sensitivity. However, most imaging methods in literature rely on a fluorescent covalent labelling of the system. Therefore, the main aim of this project was to synthetise a biocompatible fluorogenic hyaluronan probe (HA) polymer functionalised with a rhomadine B (RB) moieties and study its behaviour as an optical probe with different materials with microscopy techniques. A derivatization of HA with RB (HA-RB) was successfully obtained providing a photophysical characterization showing a particular fluorescence mechanism of the probe. Firstly, we tested the interaction with different lab-grade micro and nanoplastics in water. Thanks to the peculiar photophysical behaviour of the probe nanoplastics can be detected with confocal microscopy and more interestingly their nature can be discriminated based on the fluorescence lifetime decay with FLIM microscopy. After, the interaction of a model plant derived metabolic enzyme GAPC1 undergoing oxidative-triggered aggregation was explored with the HA-RB. We highlighted the probe interaction with the protein even at early stage of the kinetic. Moreover, nanoparticle tracking analysis (NTA) experiment demonstrates that the probe is in fact able to interact with the small pre-aggregates in the early stage of the aggregation kinetic. Ultimately, we focused on the possibility to apply the probe in a super resolution microscopy technique, PALM, exploiting its aspecific interaction to characterize the surface topography of PTFE polydisperse microplastics. Optimal conditions were reached at high concentration of the probe (70 nM) where 0.5-5 nM is always advisable for this technique. Thanks to the polymeric nature and fluorescence mechanism of the probe, this technique was able to reveal features of PTFE surface under the diffraction limit (< 250 nm).

Latent representations for traditional music analysis and generation

We create and study a generative model for Irish traditional music based on Variational Autoencoders and analyze the learned latent space trying to find musically significant correlations in the latent codes' distributions in order to perform musical analysis on data. We train two kinds of models: one trained on a dataset of Irish folk melodies, one trained on bars extrapolated from the melodies dataset, each one in five variations of increasing size. We conduct the following experiments: we inspect the latent space of tunes and bars in relation to key, time signature, and estimated harmonic function of bars; we search for links between tunes in a particular style (i.e. "reels'") and their positioning in latent space relative to other tunes; we compute distances between embedded bars in a tune to gain insight into the model's understanding of the similarity between bars. Finally, we show and evaluate generative examples. We find that the learned latent space does not explicitly encode musical information and is thus unusable for musical analysis of data, while generative results are generally good and not strictly dependent on the musical coherence of the model's internal representation.

Calibration of design strength values of Wire and Arc Additive Manufacturing inclined bars and intersections

Although being studied only for few years, Wire and Arc Additive Manufacturing (WAAM) will become the predominant way of producing stainless-steel elements in a near-like future. The analysis and study of such elements has yet to be defined in a proper way, but the projects regarding this subject are innovating more and more thanks to the findings discovered by the latter. This thesis is focused on an initial stage on the analysis of mechanical and geometrical properties of such stainless-steel elements produced by MX3D laboratories in Amsterdam, and to perform a calibration of the design strength values by means of Annex D of Eurocode 0, which talks about the analysis of the semi-probabilistic safety factors, hence the definition of characteristic values. Moreover, after testing the stainless-steel specimens by means of strain gauges and after obtaining mechanical and geometrical properties, a statistical analysis of such properties and an evaluation of characteristic values is performed. After this, there is to execute the calibration of design strength values of WAAM inclined bars and intersections.

Thermodynamics of hydrogen absorption in Mg thin films and multilayers studied by electrochemical method

Electrochemical hydrogen loading is a technique used to produce and study the hydrogenation in metals starting from a liquid solution containing water. It is a possible alternative to another, well-established technique which loads hydrogen starting from its gas phase. In this work, the electrochemical method is used to understand the fundamental thermodynamics of hydrogen loading in constraint systems such as thin films on substrates, and possibly distinguish the role of interfaces, stresses and microstructure during the hydrogenation process. The systems under study are thin films of Pd, Mg/Pd, and Ti/Mg multilayers. Possible future technological applications may be in the field of hydrogen storage and hydrogen sensors. Towards the end, the experimental setup is modified by introducing an automatic relay. This change leads to improvements in the data analysis and in the attainable information on the kinetics of the systems.

Survival Extrapolation In The Presence Of Cause Specific Hazards.

Health economic evaluations require estimates of expected survival from patients receiving different interventions, often over a lifetime. However, data on the patients of interest are typically only available for a much shorter follow-up time, from randomised trials or cohorts. Previous work showed how to use general population mortality to improve extrapolations of the short-term data, assuming a constant additive or multiplicative effect on the hazards for all-cause mortality for study patients relative to the general population. A more plausible assumption may be a constant effect on the hazard for the specific cause of death targeted by the treatments. To address this problem, we use independent parametric survival models for cause-specific mortality among the general population. Because causes of death are unobserved for the patients of interest, a polyhazard model is used to express their all-cause mortality as a sum of latent cause-specific hazards. Assuming proportional cause-specific hazards between the general and study populations then allows us to extrapolate mortality of the patients of interest to the long term. A Bayesian framework is used to jointly model all sources of data. By simulation, we show that ignoring cause-specific hazards leads to biased estimates of mean survival when the proportion of deaths due to the cause of interest changes through time. The methods are applied to an evaluation of implantable cardioverter defibrillators for the prevention of sudden cardiac death among patients with cardiac arrhythmia. After accounting for cause-specific mortality, substantial differences are seen in estimates of life years gained from implantable cardioverter defibrillators.