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Low-molecular-weight gels: from the rational design to the application of versatile soft materials
Low-molecular-weight (LMW) gels are a versatile class of soft materials that gained increasing interest over the last few decades. They are made of a small percentage, often lower than 1.0 %, of organic molecules called gelators, dispersed in a liquid medium. Such molecules have a molecular weight usually lower than 1 kDa.
The gelator molecules start to interact after the addition of a trigger, and form fibres, whose entanglement traps the solvent through capillary forces.
A plethora of LMW gelators have been designed, including short peptides. Such gelators present several advantages: the synthesis is easy and can be easily scaled up; they are usually biocompatible and biodegradable; the gelation phenomenon can be rationalised by making small variation on the peptide scaffold; they find application in several fields.
In this thesis, an overview of several peptide based LMW gels is presented. In each study, the gelation conditions were carefully studied, and the final materials were thoroughly investigated. First, the gelation ability of a fluorinated phenylalanine was assessed, to understand how the presence of a rigid moiety and the presence of fluorine may influence the gelation. In this context, a method for the dissolution of sensitive gelators was studied. Then, the control over the gel formation was studied both over time and space, taking advantage of either the pH-annealing of the gel or the reaction-diffusion of a hydrolysing reagent.
Some gels were probed for various applications. Due to their ability of trapping water and organic solvents, we used gels for trapping pollutants dissolved in water, as well as a medium for the controlled release of either fragrances or bioactive compounds. Finally, the interaction of the gel matrix with a light-responsive molecule was assessed to understand wether the gel properties or the interaction of the additive with light were affected
The transformative potential of community engagement in higher education: an analysis of service-learning effects on students, communities, and institutions.
Service-learning in higher education is gaining attention as a reliable tool to support students’ learning and fulfil the mission of higher education institutions (HEIs). This dissertation addresses existing gaps in the literature by examining the effects and perspectives of service-learning in HEIs through three studies.
The first study compares the effects of a voluntary semester-long service-learning course with traditional courses. A survey completed by 110 students before and after the lectures found no significant group differences in the psychosocial variables under inspection. Nevertheless, service-learning students showed higher scores concerning the quality of participation. Factors such as students’ perception of competence, duration of service-learning, and self-reported measures may have influenced the results.
The second study explores the under-researched perspective of community partners in higher education and European settings. Twelve semi-structured interviews were conducted with community partners from various community organisations across Europe. The results highlight positive effects on community members and organisations, intrinsic motivations, organisational empowerment, different forms of reciprocity, the co-educational role of community partners, and the significant role of a sense of community and belonging.
The third study focuses on faculty perspectives on service-learning in the European context. Twenty-two semi-structured interviews were conducted in 14 European countries. The findings confirm the transformative impact of service-learning on the community, students, teachers, and HEIs, emphasising the importance of motivation and institutionalisation processes in sustaining engaged scholarship. The study also identifies the relevance of the community experience, sense of community, and community responsibility with the service-learning experience; relatedness is proposed as the fifth pillar of service-learning.
Overall, this dissertation provides new insights into the effects and perspectives of service-learning in higher education. It integrates the 4Rs model with the addition of relatedness, guiding the theoretical and practical implications of the findings. The dissertation also suggests limitations and areas for further research
Innovation and inclusion in school: can innovative spaces and didactics in a school open to the community favour the inclusion of all the students? The perceptions of Headteachers, teachers and students
La ricerca, di carattere esplorativo, prende spunto dal dibattito internazionale, sviluppatosi sul finire dello scorso secolo, sulla necessità di innovare il sistema educativo, in ottica di lifelong-learning, e favorire l’acquisizione delle competenze richieste nel XXI secolo. Le diverse indicazioni sollecitano una scuola intesa come Civic-center in grado di riconoscere gli apprendimenti extra-scolastici, con spazi di apprendimento innovativi funzionali a didattiche learner-centred. A circa trent’anni dalla Dichiarazione di Salamanca riteniamo necessario interrogarsi se queste innovazioni garantiscano l’inclusione e il successo formativo di tutti. La ricerca si articola in quattro studi di caso relativi a due scuole secondarie di secondo grado innovative italiane e due finlandesi. Si propone di comprendere sulla base delle percezioni di studenti, insegnanti, dirigenti se tale modello di scuola favorisca anche l’inclusione e il benessere di tutti gli studenti. Dall’analisi dei risultati sembra che, secondo le percezioni di coloro che hanno partecipato alla ricerca, le scuole siano riuscite a far coesistere innovazione e inclusione. In particolare, l’utilizzo di spazi di apprendimento innovativi e didattiche learner-centred all’interno di una scuola aperta al territorio in grado di riconoscere le competenze extra-scolastiche, sembrano favorire effettivamente l’inclusione di tutti gli studenti. Nonostante gli aspetti innovativi, restano tuttavia presenti all’interno delle scuole analizzate ancora diverse criticità che non consentono una piena inclusione for allThis exploratory research, has as a starting point the international debate, developed at the end of the last century, on the necessity of bringing innovation into the educational system both from a perspective of lifelong-learning and to favour the acquisition of 21st Century competences. Recommendations call for schools intended as Civic-centers able to recognise extra-school learning, and with innovative learning spaces designed for learner-centred didactics. Thirty years on from the Salamanca Declaration we are exploring how far these innovations can guarantee inclusion and educational achievement for all. This research is articulated through the presentation of four case studies: two innovative high schools in Italy, and two in Finland. It intends to understand, through collecting the perceptions of the students, teachers, and principals, if these school models also favour the inclusion and well-being of all the students. Based on the analysis of the results it appears that, according to the perceptions of the research participants, the schools have achieved the co-existence of both innovation and inclusion. In particular the use of innovative learning spaces and learner-centred didactic, in a school that is also open to the territory/community and able to recognise extra-school learning, appear to favour the inclusion of all students. Innovative aspects notwithstanding, there nevertheless remain certain critical issues that do not allow the achievement of full inclusion for all
Trajectory planning of single and dual-arm robots for time-optimal handling of liquids and objects
This Thesis studies the optimal control problem of single-arm and dual-arm serial robots to achieve the time-optimal handling of liquids and objects.
The first topic deals with the planning of time-optimal anti-sloshing trajectories of an industrial robot carrying a cylindrical container filled with a liquid, considering 1-dimensional and 2-dimensional planar motions. A technique for the estimation of the sloshing height is presented, together with its extension to 3-dimensional motions. An experimental validation campaign is provided and discussed to assess the thoroughness of such a technique. As far as anti-sloshing trajectories are concerned, 2-dimensional paths are considered and, for each one of them, three constrained optimizations with different values of the sloshing-height thresholds are solved. Experimental results are presented to compare optimized and non-optimized motions.
The second part focuses on the time-optimal trajectory planning for dual-arm object handling, employing two collaborative robots (cobots) and adopting an admittance-control strategy. The chosen manipulation approach, known as cooperative grasping, is based on unilateral contact between the cobots and the object, and it may lead to slipping during motion if an internal prestress along the contact-normal direction is not prescribed. Thus, a virtual penetration is considered, aimed at generating the necessary internal prestress. The stability of cooperative grasping is ensured as long as the exerted forces on the object remain inside the static-friction cone. Constrained-optimization problems are solved for 3-dimensional paths: the virtual penetration is chosen among the control inputs of the problem and friction-cone conditions are treated as inequality constraints. Also in this case experiments are presented in order to prove evidence of the firm handling of the object, even for fast motions
Understanding food waste through behavioural theories in different settings
SDG 12.3 aims to promote sustainable consumption and production patterns by addressing the global food loss and waste problem. Given the multiple interrelated impacts, food waste is recognized as one of the major food system challenges. The scope of this work is to contribute to the understanding on food waste generation and potential approaches to tackle it. This work was specifically designed to achieve the following goals: 1) Understand specific factors that affect individual behaviours to generate FW at household, 2) Analyse the effective ways to reduce FW through behaviour change perspective given the catering and hospitality sector, and 3) Provide an evidence synthesis on intervention study that incorporate stakeholder insights focus on school meals. The first goal of identifying food waste drivers was achieved by the systematically reviewing on peer-reviewed and grey literature. The Motivation-Opportunity-Ability (MOA) framework was applied to frame consumer behavioural drivers and identify levers that could be potentially utilized to reduce food waste. Consumer segmentation was further discussed to provide insights for developing tailored food waste reduction interventions. The second goal required the identification on practical interventions, which has been accomplished by systematic literature review basing on the Preferred Reporting Items for Systematic Reviews and Meta-Analyses. The efficiency and working mechanism of interventions were evaluated basing on the combination of MOA and behavioural change wheel. Building on the evidence of effective interventions, a roadmap was developed for policymakers and practitioners to lead their own pathway on intervention study and upscaling. The third aim has been achieved with a school meals interventions mapping and the implementation of stakeholder workshops. The method was built on the literature review and then enriched by intervention co-design dialogue among stakeholders. The overall conclusion addressed challenges of food waste determents identification, tailored reduction interventions developing, sustainable consumption promotion with school meals
Nature in the books of seven metals – Ǧābirian corpus in dialogue with ancient Greek philosophy and Byzantine alchemy –
The Ǧābirian corpus was a receiver of ancient Greek ideas and, at the same time, a source of knowledge for the later Greek-speaking world, in particular for medieval Byzantine alchemy. Both aspects are explored in the dissertation with respect to the notion of nature. After a general introduction to the Corpus and the sciences described in it, particular attention is devoted to a Byzantine anonymous text, The Work of Four Elements, which was probably influenced by the Ǧābirian Books of Seventy. These texts exemplify how, in the theory of the Ǧābirian science, things are constructed from four natures (hot, cold, moist and dry), the balance of which defines what a thing is. By changing the balance of natures, one can transmute any metals into gold that is perfectly proportioned in terms of natures. Ǧābir presents the art of dyeing metals gold in the Books of Seven Metals which, along with chrysopoetic recipes, also include medical recipes and theoretical contents such as the theories of four humours, properties, and talismans. Moreover, Ǧābir postulated a substrate that does not change in itself and continues to exist when natures move in and out of things. Such primary existence is called the fifth nature as an additional principle to the four natures. This key concept for the Ǧābirian theory, which has been underexplored so far, is discussed through the textual and critical analysis of various unedited sources: the Books of Seven Metals and the Book of the Fifth Nature. This study confirms that the fifth nature was probably derived from ancient Greek philosophical concepts such as the Empedoclean particles, the Aristotelian fifth element and the Stoic pneuma. Thus, this research indicates the importance of the Ǧābirian corpus both in the history of alchemy and the history of philosophy
Impact of Geomatic Techniques on Topo-Bathymetric Surveys for Coastal Analysis
Sandy coasts represent vital areas whose preservation and maintenance also involve economic and tourist interests. Besides, these dynamic environments undergo the erosion process at different levels depending on their specific characteristics. For this reason, defence interventions are commonly realized by combining engineering solutions and management policies to evaluate their effects over time. Monitoring activities represent the fundamental instrument to obtain a deep knowledge of the investigated phenomenon. Thanks to technological development, several possibilities both in terms of geomatic surveying techniques and processing tools are available, allowing to reach high performances and accuracy. Nevertheless, when the littoral definition includes both emerged and submerged beaches, several issues have to be considered. Therefore, the geomatic surveys and all the following steps need to be calibrated according to the individual application, with the reference system, accuracy and spatial resolution as primary aspects. This study provides the evaluation of the available geomatic techniques, processing approaches, and derived products, aiming at optimising the entire workflow of coastal monitoring by adopting an accuracy-efficiency trade-off. The presented analyses highlight the balance point when the increase in performance becomes an additional value for the obtained products ensuring proper data management. This perspective can represent a helpful instrument to properly plan the monitoring activities according to the specific purposes of the analysis. Finally, the primary uses of the acquired and processed data in monitoring contexts are presented, also considering possible applications for numerical modelling as supporting tools. Moreover, the theme of coastal monitoring has been addressed throughout this thesis by considering a practical point of view, linking to the activities performed by Arpae (Regional agency for prevention, environment and energy of Emilia-Romagna). Indeed, the Adriatic coast of Emilia-Romagna, where sandy beaches particularly exposed to erosion are present, has been chosen as a case study for all the analyses and considerations
Impact of gentrification processes in rural landscapes: a methodology for landscape assessment towards sustainable rural development
With an increasing demand for rural resources and land, new challenges are approaching affecting and restructuring the European countryside. While creating opportunities for rural living, it has also opened a discussion on rural gentrification risks. The concept of rural gentrification encircles the influx of new residents leading to an economic upgrade of an area making it unaffordable for local inhabitants to stay in.
Rural gentrification occurs in areas perceived as attractive. Paradoxically, in-migrants re-shape their surrounding landscape. Rural gentrification may not only cause displacement of people but also landscape values. Thus, this research aims to understand the twofold role of landscape in rural gentrification theory: as a possible driver to attract residents and as a product shaped by its residents.
To understand the potential gentrifiers’ decision process, this research has provided a collection of drivers behind in-migration. Moreover, essential indicators of rural gentrification have been collected from previous studies. Yet, the available indicators do not contain measures to understand related landscape changes. To fill this gap, after analysing established landscape assessment methodologies, evaluating the relevance for assessing gentrification, a new Landscape Assessment approach is proposed. This method introduces a novel approach to capture landscape change caused by gentrification through a historical depth.
The measures to study gentrification was applied on Gotland, Sweden. The study showed a population stagnating while the number of properties increased, and housing prices raised. These factors are not indicating positive growth but risks of gentrification. Then, the research applied the proposed Landscape Assessment method for areas exposed to gentrification. Results suggest that landscape change takes place on a local scale and could over time endanger key characteristics. The methodology contributes to a discussion on grasping nuances within the rural context. It has also proven useful for indicating accumulative changes, which is necessary in managing landscape values
Study and implementation of control strategies for polymerization processes assisted by atmospheric pressure plasma jets
In recent years, polymerization processes assisted by atmospheric pressure plasma jets (APPJs) have received increasing attention in numerous industrially relevant sectors since they allow to coat complex 3D substrates without requiring expensive vacuum systems. Therefore, advancing the comprehension of these processes has become a high priority topic of research. This PhD dissertation is focused on the study and the implementation of control strategies for a polymerization process assisted by an atmospheric pressure single electrode plasma jet. In the first section, a study of the validity of the Yasuda parameter (W/FM) as controlling parameter in the polymerization process assisted by the plasma jet and an aerosolized fluorinated silane precursor is proposed. The surface characterization of coatings deposited under different W/FM values reveals the presence of two very well-known deposition domains, thus suggesting the validity of W/FM as controlling parameter. In addition, the key role of the Yasuda parameter in the process is further demonstrated since coatings deposited under the same W/FM exhibit similar properties, regardless of how W/FM is obtained. In the second section, the development of a methodology for measuring the energy of reactions in the polymerization process assisted by the plasma jet and vaporized hexamethyldisiloxane is presented. The values of energy per precursor molecule are calculated through the identification and resolution of a proper equivalent electrical circuit. To validate the methodology, these energy values are correlated to the bond energies in the precursor molecule and to the properties of deposited thin films. It is shown that the precursor fragmentation in the discharge and the coating characteristics can be successfully explained according to the obtained values of energy per molecule. Through a detailed discussion of the limits and the potentialities of both the control strategies, this dissertation provides useful insights into the control of polymerization processes assisted by APPJs
Role of Shiga toxins in the pathogenesis of hemolytic uremic syndrome
During the pathogenesis of hemolytic uremic syndrome (HUS), a severe sequela of Shiga toxin (Stx)-producing Escherichia coli (STEC) gastrointestinal infections, before the toxin acts on the target endothelial cells of the kidney and brain, several Stx forms are transported in the bloodstream: free Stx; Stx bound to circulating cells through Gb3Cer and TLR4 receptors; and Stx associated to blood cell-derived microvesicles. The latter form is mainly responsible for the development of life-threatening HUS in 15% of STEC-infected patients. Stx consist of five B subunits non-covalently bound to a single A subunit (uncleaved Stx) which can be cleaved in two fragments (A1 and A2) held by a disulfide bond (cleaved Stx). After reduction, the enzymatically active A1 fragment responsible for toxicity is released. Cleaved and uncleaved Stx are biologically active but functionally different, thus their presence in patients’ blood could affect the onset of HUS. Currently, there are no effective therapies for the treatment of STEC-infected patients and the gold standard strategies available for the diagnosis are very expensive and time-consuming.
In this thesis, by exploiting the resolving power of SERS technology (Amplified Raman Spectroscopy on Surfaces), a plasmonic biosensor was developed as effective diagnostic tool for early detection of Stx in patients’ sera. An acellular protein synthesis system for detecting cleaved Stx2a in human serum based on its greater translation inhibition after treatment with reducing agents was developed and used to identify cleaved Stx in STEC-infected patients’ sera. Pathogenic microvesicles from Stx2a-challenged blood from healthy donors were isolated and characterized. The antibiotic NAB815, acting as inhibitor of toxin binding to TLR4 expressed by circulating cells, was found to be effective in impairing the formation of blood cell-derived microvesicles containing Stx2a, also having a protective effect in cellular models. This approach could be proposed as an innovative treatment for HUS prevention